JP2008524391A - Films produced from polymer blends - Google Patents

Abstract

Isotactic polypropylene and ethylene / propylene polymers are often used in industries that produce commodities such as fibers, films, molded parts and nonwovens. Furthermore, blending these polymers with other polymers has also been the subject of research so far.
It has been suggested that the addition of an ethylene and propylene stereoblock copolymer to isotactic polypropylene improves the mechanical properties of the blend compared to isotactic polypropylene alone.
The present invention provides a heterogeneous blend comprising one or more semi-crystalline polymers and one or more semi-amorphous polymers, with a balanced combination of toughness, flexibility and transparency, and further under polypropylene conditions. A blend capable of maintaining crystallinity that can be processed with a film and a film comprising the blend is provided.
[Selection] Figure 1

Description

The present invention relates to heterogeneous polymer blends and films made therefrom.

The present invention claims priority from US patent application 60 / 637,429 filed on December 17, 2004 and US patent application 60 / 655,310 filed February 22, 2005.

  This application is related to US patent application 10 / 716,306 filed on November 18, 2003. The present invention also relates to co-pending US patent application 10 / 402,275 filed on March 28, 2003.

Isotactic polypropylene and ethylene / propylene polymers are often used in industries that produce commodities such as fibers, films, molded parts and nonwovens. Furthermore, blending these polymers with other polymers has also been the subject of research so far.

For example, US Pat. No. 3,262,992 shows that the addition of a stereoblock copolymer of ethylene and propylene (which has a high crystalline melting point) to isotactic polypropylene improves the mechanical properties of the blend compared to isotactic polypropylene alone. Suggests.

US Pat. Nos. 3,853,969 and 3,378,606, suggest the generation of in situ blends of isotactic polypropylene and “stereoblock” copolymers of other olefins with 2 to 12 carbons, including propylene and ethylene and hexene. To do.

US Pat. No. 3,82,191 suggests a propylene / alphaolefin copolymer with stereoregularity, a blend of propylene and ethylene copolymer rubber with stereoregularity.

U.S. Pat.No. 3,888,949 includes isotactic polypropylene and copolymers of propylene and alpha olefins, having between 6 and 20 carbon atoms, and has a higher elongation and tensile strength than simply copolymer or isotactic polypropylene. Suggestions are given for composites of improved blend composition, describing copolymers of propylene and alpha olefins in which the alpha olefin is hexene, octene or dodecene.

U.S. Pat.No. 4,461,872, discloses blends produced in part by using other heterogeneous catalyst systems that are expected to produce copolymers with statistically significant intra- and intermolecular compositional differences. .

Two articles in the Journal of Macromolecules, 1989, Vol. 22, pages 3851-3866, disclose blends of isotactic polypropylene and partially atactic polypropylene that are said to have desirable tensile elongation properties. is doing.

US Pat. Nos. 5,723,217; 5,726,103; 5,736,465; 5,763,080 and 6,010,588 suggest a process using several metallocene catalysts to make polypropylene to produce fibers and fabrics. US Pat. No. 5,891,814 discloses a propylene polymer produced by a binary metallocene used to produce spunbond fibers. WO 99/19547 discloses a method for producing spunbond fibers and fabrics derived from blends of propylene homopolymer and polypropylene copolymer.

US Pat. No. 6,342,565 and the corresponding WO 00/070134 have Tables 24, 24 with 80, 90, and 95 wt% Achieve 3854, and 13.5% ethylene and 12 ML, respectively, 20, 10 and Disclosed are fibers comprising copolymers each containing 5 wt% propylene / ethylene. These special blends are not used as films, molded goods or nonwoven materials. The fibers in Table 4 are reported to be inelastic and are unsuitable for application as the desired elastic material in US Pat. No. 6,342,565.

U.S. Patents 6,525,157, 5,504,172; and WO 00/070134 disclose various propylene / ethylene copolymers. US Patent Application 2003/0130430 discloses a blend of two different propylene / ethylene copolymers. US Patents 6,642,316, WO 00/070134, WO 00/01766, US Patents 6,500,563 and 6,342,565, and WO 00/69963 disclose elastic blends of crystalline polypropylene and propylene / ethylene copolymers. US Pat. No. 6,153,703 discloses a blend of semicrystalline copolymer and propylene ethylene polymer that has very high toughness but does not lose modulus. EP 0 629 632 and EP 0629 631 disclose blends of polypropylene and ethylene-propylene copolymer with certain triadic stereoregularity and the proportion of propylene units inserted back.

US Pat. No. 6,635,715 and its corresponding patents EP 1 003 814 Bl and WO 99/07788 disclose a blend of Escorene 4292 with polypropylene and propylene / ethylene copolymers for use as thermoplastic elastomers.

EP 0 374 695 Al discloses a visually homogeneous blend of an ethylene-propylene copolymer and Basell's Profax® 6331.
US Pat. No. 6,750,284 discloses a thermoplastic film comprising a propylene-ethylene copolymer and up to 40% by weight polypropylene.

WO 03/040095; WO 03/040201, WO 03/040233, and WO 03/040442 disclose various propylene-ethylene copolymers made with non-metallocene catalyst compounds. WO 03/040202 discloses films and sealants made from propylene-ethylene copolymers made with nonmetallocene catalyst compounds. Further references of interest include WO 94/28042, EP 1 002 814, WO 00/69965, WO 01/48034, WO 04035681A2, EP 0 400 333 Bl, EP 0 373 660 Bl, WO 04060994A1, US patent. There are 5,453,318, 5,298,561, and 5,331,047.

The present invention also relates to co-pending US patent application 10 / 402,275 filed on March 28, 2003.

However, none of the documents disclosed above can maintain a crystallinity that can be further processed under polypropylene conditions, while having a balanced combination of toughness, flexibility and transparency. None disclose possible blends.

Summary of the Invention

The present invention relates to a film comprising a heterogeneous blend including:
1) 60 to 99 wt% of one or more semicrystalline polymers (based on the weight of semicrystalline and semiamorphous polymers), each semicrystalline polymer comprising propylene and 0 to 5 wt% alpha olefin comonomer ( Said semi-crystalline polymers each having a melting point between 100 and 170 ° C. and a melt flow rate of 200 dg / min or less (preferably 50 dg / min or less); and 2) one or more 1 to 40% by weight of semi-amorphous polymer (based on the weight of semi-crystalline and semi-amorphous polymer), each semi-amorphous polymer being propylene and 10 to 25% by weight of one or more C2 and / or Comprising C4 to C10 alpha-olefin comonomers, each of the semi-amorphous polymers having:
a) a heat of fusion of 4 to 70 J / g;
b) a melt flow rate of 0.1 to 200 dg / min (preferably less than 50 dg / min); and
c) Intermolecular component distribution determined by thermal fractionation in hexane, where more than 85% by weight of the polymer is separated as one or two adjacent soluble parts, and the rest of the polymer is immediately before or after Each of these parts is in a range where the weight percent comonomer content does not exceed 20 weight percent relative to the average weight percent comonomer content of the copolymer; and
d) Mw / Mn is 1.5 to 4; and
e) Propylene triple stereoregularity measured by ¹³ C NMR is 75% or more,
The blend is:
i) a melt flow rate of 0.1 to 50 dg / min (preferably 0.1 to 20 dg / min);
ii) less than 5% by weight filler based on the weight of polymer and filler;
iii) The haze measured with a 1 mm thick injection molded chip is less than 20%, and
iv) The permanent set is greater than 65%; and the film has a thickness of 0.1 to 25 mils (2.5 to 635 microns):
Haze is less than 10%, and
Secant tensile modulus is about 100,000 to about 30,000 psia (about 690 to about 207 MPa), and Elmendorf tear strength in the machine direction is 45 g / mil or more (1.77 g / micron or more) And a transverse Elmendorf tear strength of 45 g / mil or more (1.77 g / micron or more) and a total energy impact of 3 ft.lb or more (4.0 J or more) and
45 degree gloss has 82 units or more.

In certain preferred embodiments, the semi-crystalline and semi-amorphous polymers are heterogeneous blends, preferably the semi-crystalline polymer is the continuous phase and the semi-amorphous polymer is the discontinuous phase.

The term heterogeneous blend means that compositions having two or more morphological phases are in the same state. For example, a blend of two polymers, in which one polymer of them forms a separated small packet dispersed in a matrix of another polymer, is said to be heterogeneous in the solid state. Heterogeneous blends are also defined to include co-continuous blends where it can be clearly seen that the blend components are separated, but which is the continuous phase and which is not the discontinuous phase. Such morphology is determined using scanning electron microscopy (SEM) or atomic force microscopy (AFM), and SEM should be used when SEM and AFM show different data It is. The term continuous phase refers to the matrix phase being in a heterogeneous blend. The term discontinuous phase means that the dispersed phase is in a heterogeneous blend. The term homogeneous blend means that compositions having substantially one morphological phase are in the same state. For example, a blend of two polymers in which one polymer is miscible with another polymer can be said to be uniform in the solid state. Such morphology is determined by scanning electron microscopy. The term miscible refers to two or more polymers exhibiting single-phase behavior at the glass transition temperature, eg, Tg appears to exist as a single distinct transition temperature in the DMTA trace. In contrast, for immiscible blends, it appears that two separate transition temperatures are usually observed corresponding to the individual components of the blend. Thus, the polymer blend is miscible when one Tg appears in the DMTA trace. The blend that is miscible is uniform, while the immiscible blend is heterogeneous.

Detailed Description of the Invention

For the purposes of the present invention and in the context of the claims, a copolymer refers to any polymer containing two or more monomers. When a polymer is said to contain a monomer, the monomer present in the polymer is the polymerized form of the monomer. Similarly, when a catalyst component is said to contain a neutral, stable form of the component, it is well understood by those skilled in the art that the activated form of the component is the form that reacts with the monomer to form a polymer. It is that you are.

The new group numbers in the periodic table used in this specification are those specified in CHEMICAL AND ENGINEERING NEWS, 63 (5), 27 (1985).

As used herein, a film is an extruded or other process whose thickness is a major factor, whose thickness is uniform and in the range of 0.1 to 25 mils (2.5 to 635 μm). Applies to products processed by

A film can be a single layer or part of a combination (multilayer) of layers. Single or multilayer films can be laminated to other cast single or multilayer films by extrusion lamination or other methods. The film can be made by any industry recognized processing method such as film molding or film blowing.

As used herein, “polypropylene”, “propylene polymer” or “PP” refers to homopolymers, copolymers, terpolymers and interpolymers containing 50 to 100% by weight of propylene.

As used herein, “reactor grade” refers to its molecular weight distribution (MWD) or polydispersity, except when pelleted with an antioxidant after polymerization. Refers to a polyolefin resin that is essentially unchanged. The term specifically includes polyolefins that have not been or have not been subjected to treatments that significantly reduce viscosity or significantly reduce average molecular weight after polymerization.

As used herein, a “metallocene” is one or more compounds represented by the chemical formula Cp _m MR _n X _q , where Cp is a cyclopentadienyl ring, which may be substituted. Or derived from one that may be substituted (eg, indene or fluorene); M is, for example, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, and tungsten. Such as Group 4, 5 or 6 transition metals; R is a substituted or unsubstituted hydrocarbyl or hydrocarboxyl group having 1 to 20 carbon atoms; X is halide, hydrogen May be a compound, an alkyl group, an alkenyl group, or an arylalkyl group; m = 1-3; n = 0-3; q = 0-3; And if m is 2 or 3, then any two Cp groups may be linked to each other through a bridging group T, where T is typically 14 groups that may be substituted with one or two hydrocarbyl groups (preferred examples include (CH ₃ ) ₂ —Si), and if m is 1, the Cp group is a bridging group. (A bridging group) may be bonded to R through T, which is typically substituted with one or two hydrocarbyl groups (preferred examples include (CH ₃ ) ₂ —Si). There are sometimes 14 atomic groups.

Abbreviations are used including Me = methyl, Et = ethyl, Bu = butyl, Ph = phenyl, Cp = cyclopentadienyl, Cp * = pentamethylcyclopentadienyl, Ind = indenyl, Flu = fluorene.

“Support” or “support composition” refers to particulate and porous compounds that are optionally calcined or contacted with a halogen. For example, the fluoride-carrying composition may be a silicon dioxide carrier in which part of the silica hydroxyl group is substituted with fluorine or a compound containing fluorine. Suitable fluorine-containing compounds include, but are not limited to, compounds containing inorganic fluorine and / or compounds containing organic fluorine.

As used herein, a “metallocene catalyst system” includes (1) one or more metallocenes; (2) one or more activators; and (3) optionally, one or more supported compositions; It is a product of each contacting component. Preferred activators include alumoxanes (including methylaluminoxane, modified methylaluminoxane), stoichiometric activators, ionic activators, non-coordinating anions, and the like.

As used herein, a “semi-crystalline polymer” is an olefin polymer having a melting point (Tm) of 100 ° C. or higher (measured by DSC-second melt described below). Is defined. As used herein, a “semi-amorphous polymer” is defined as an olefin polymer (measured by DSC described below) having a heat of fusion between 4 and 70 J / g. Melting point (Tm), peak crystallization temperature (Tc), heat of fusion (Hf) and% crystallinity are determined according to ASTM E 794-85 using the following procedure. Data from a differential scanning calorimeter (DSC) is obtained using a TA Instruments instrument model 2910 (TA Instruments 2910 machine) or a Perkin-Elmer DSC 7 instrument. If the TA instrument model 2910 and the Perkin-Elmer DSC 7 instrument give different data, the TA instrument model 2910 data should be used. Approximately 5-10 mg of sample is enclosed in an aluminum sample pan. DSC data is recorded by first cooling the sample to −50 ° C. and gradually heating to 200 ° C. at a rate of 10 ° C./min. The sample is kept at 200 ° C. for 5 minutes before being subjected to a second cooling-heating cycle. Thermal events for the first and second cycles are recorded. The area of the dissolution curve is measured and used to determine the heat of fusion and crystallinity.

Crystallinity% (X%) is calculated using the following formula:
X% = [area in curve (joule / gram) / B (joule / gram)] * 100, where B is the heat of fusion of the homopolymer of the main monomer component. These figures for B can be taken from John Wiley and Sons, New Yark 1999 publication Polymer Handbook, 4th edition. A value of 189 J / g (B) is used as the heat of fusion of 100% crystalline polypropylene. For semicrystalline polymers with substantial crystallinity, the melting temperature is usually measured and reported during the second thermal cycle (or second melting).

For semi-amorphous polymers with a relatively low level of crystallinity, the melting temperature is usually measured and reported during the first thermal cycle. Prior to DSC measurement, the sample is aged (usually by placing it at ambient temperature for up to about 5 days) or annealed to maximize crystallinity.

The molecular weights (Mn and Mw) and molecular weight distributions (MWD or Mw / Mn) used herein are determined by gel permeation chromatography (Gel Permeation Chromatography (GPC)) using polystyrene standards. GPC data was collected on a Waters 150 GPC using three Shodex mixed bed AT-80M / S columns. The solvent used is 1,2,4 trichlorobenzene with 300 ppm antioxidant, Santonox R ,. The operating conditions were an operating temperature of 145 ° C., a nominal flow rate of 1.0 ml / min and an injection volume of 300 μL. The amount of infusion solution was typically 1.0 to 1.5 mg / ml. The column was measured using a series of narrow molecular weight polystyrene (PS) standards and calibrated by recording the retention volume. Polypropylene (PP) molecular weight was calculated using the “universal calibration” approach and the following (Mark-Houwink) factor.

k (d / Lg) a
PS 1.75 X 10 ^-4 0.67
PP 8.33 x 10 ^-5 0.80
A third order fit is used to fit log (MW) versus retention capacity points. Data was collected and analyzed by Waters Millenium software.

Clarifying agent has at least 10%, preferably haze (measured on 1 mm molded chip according to (ASTM D 1003)) compared to the same composition without clarifier All fining agents are defined as reducing by 15%, more preferably by at least 20%. The nucleating agent is often a clarifying agent. Nucleating agents are defined as additives that form nuclei during polymer dissolution that promote crystal growth (such as adipic acid, benzoic acid, or metal salts of these acids, such as 3,4-dimethylbenzylidene sorbitol). Sorbitol is an example of a nucleating agent as well as many inorganic fillers).

Semi-crystalline polymer blend composition In certain preferred embodiments, the blends of the present invention comprise 60 to 99% by weight of one or more semi-crystalline polymers (based on the weight of semi-crystalline and semi-amorphous polymers). , Preferably 60 to 90% by weight, preferably 60 to 85% by weight, preferably 60 to 75% by weight, each semi-crystalline polymer being propylene and 0 to 5% by weight of alpha olefin comonomer (based on the weight of the polymer) ), Preferably 0.1 to 4% by weight, preferably 0.25 to 3% by weight. Preferably the alpha olefin comonomer is a C2 to C10 alpha olefin, preferably consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, and decene, preferably ethylene, butene, hexene, and octene, preferably ethylene. It is good to be selected from the flock. (For purposes of the present invention, if the copolymer comprises propylene and one or more C2 to C10 olefins, or alpha olefins, the C2 to C10 olefins, or alpha olefins, do not contain C3, eg, propylene).

Preferred semi-crystalline polymers should have a melting point (Tm—second melting as measured by DSC as described above) of 100 to 170 ° C., preferably 110 to 170 ° C., preferably 125 to 170 ° C.

Preferred semi-amorphous polymers are melt flow rates of 0.1 to 200 dg / min, preferably 0.25 to 100 dg / min, preferably 0.5 to 50 dg / min, preferably 0.5 to 20 dg / min, preferably 1 to 20 dg / min. Good flow rate (ASTM 1238-D, 2.16kg, at 230 ° C).

Preferred semi-crystalline polymers have an elongation at break measured by ASTM D 638 of 0.125 inch (3.18 mm) injection molded sample at 2 inches / minute (50 mm / minute), less than 700%, Preferably it is 300 to 700%.

A preferred semicrystalline polymer has a 1-degree secant flexural modulus measured by ASTM D-790A (0.05 in / min, 1.3 mm / min) of 100,000 to 250,000 psi (690 to 1720 MPa), preferably Should be 150,000 to 250,000 psi (1035 to 1720 MPa). “High-crystallinity polypropylene” having, for example, a value larger than the above 250,000 psi (1720 MPa) can also be used.

Any polypropylene polymer having 0 to 5 wt% comonomer, a melting point of 100 to 170, and an MFR of 200 dg / min or less may be used in the practice of the present invention. Suitable examples include polymers produced by Ziegler-Natta catalyst systems, metallocene systems, and the like. The polymer can be produced by any method including solution, slurry, gas phase, supercritical pressure, or high pressure. In particularly preferred embodiments, the propylene polymers useful in the present invention should have a molecular weight distribution (Mw / Mn) of 5 or less, preferably between 1.5 and 4, preferably between 1.5 and 3. In other preferred embodiments, preferred propylene polymers useful in the present invention include polymers produced by metallocene catalyst systems. In other embodiments, preferred propylene polymers useful in the present invention have a composition distribution breadth index (CDBI) of 60% or more, preferably 70% or more, preferably 80% or more, preferably 90%. (CDBI is measured as described in WO 93/03093, but amended so that all parts with a weight average molecular weight (Mw) of less than 25,000 g / mol are ignored). Preferred propylene polymers used in the practice of the invention include propylene polymers sold under the trade name ACHIEVE® by ExxonMobil Chemical Company, and particularly useful grades are from ExxonMobil Chemical Company, Houston, Texas. Available ACHIEVE® 3854, ACHIEVE® 1654El, ACHIEVE® 3825, ACHIEVE® 1605. Preferred for use in the practice of the present invention Polypropylene polymers further include propylene homopolymers and random copolymers available from ExxonMobil Chemical Company under the grade names PP1024E4, PP1042, PP1032, PP1044, PP1052, PP1105El, PP3155 and PP9852El, PP9272, PP9513, PP9544, and PP9562.

In one example, impact copolymers can be used in the practice of the present invention. Some of these are available from ExxonMobil Chemical Company (eg PP7032 E2).

In other embodiments, preferred semicrystalline polymers useful in the present invention have a melting point above 110 ° C, preferably above 110 ° C, most preferably above 130 ° C, and / or by DSC analysis as described above. The determined heat of fusion is greater than 60 J / g, preferably at least 70 J / g, preferably at least 80 J / g.

The molecular weight of the semicrystalline polymer is between 10,000 and 5,000,000 gl / mol, alternatively between 50,000 and 500,000 gl / mol, preferably with a polydispersity index between 1.5 and 4, preferably between 1.5 and 3. There should be.

Preferred semicrystalline polymers may be isotactic, highly isotactic, syndiotactic, or highly syndiotactic. In some embodiments, the semicrystalline polymer is isotactic polypropylene. In other embodiments, the semicrystalline polymer is a highly isotactic polypropylene. As used herein, “isotactic” is defined as containing at least 10%, preferably at least 40%, of isotactic pentameric methyl groups derived from propylene, as analyzed by ¹³ C-NMR. The

As used herein, “highly isotactic” is defined as having at least 60% isotactic pentads as analyzed by ¹³ C-NMR. In certain desirable embodiments, the polypropylene homo- or copolymer having at least 85% isotacticity is a semi-crystalline polymer. In other embodiments, the semicrystalline polymer has at least 90% isotacticity. As used herein, “syndiotactic” is defined as having at least 10%, preferably at least 40%, of syndiotactic quintuplets as analyzed by ¹³ C-NMR. As used herein, “highly syndiotactic” is defined as having at least 60% of syndiotactic pentads as analyzed by ¹³ C-NMR. In certain desirable embodiments, the polypropylene homo- or copolymer with at least 85% syndiotacticity is a semi-crystalline polymer. In other embodiments, the propylene homo- or copolymer having at least 90% syndiotacticity is a semi-crystalline polymer.

Blends of Semi-Amorphous Polymer Components In certain preferred embodiments, the blends of the present invention contain from 1 to 40% by weight of one or more semi-amorphous polymers (based on weight to semi-crystalline and semi-amorphous polymers). 10) to 40% by weight, preferably 15 to 40% by weight, preferably 25 to 40% by weight. In certain embodiments, the semi-amorphous polymer, based on the weight of the propylene copolymer, comprises 10 to 25% by weight of one or more C2 to C10 alpha olefin comonomers, preferably 10 to 20% by weight, It is preferable to contain 12 to 20% by weight. Preferably the alpha olefin comonomer is a C2 to C10 alpha selected from the group consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, and decene, preferably ethylene, butene, hexene, and octene, preferably ethylene. It should be olefin.

The ethylene content of the semi-amorphous polymer is measured as follows. A thin homogeneous film is pressed at a temperature above about 150 ° C. and placed in a Perkin Elmer PE 1760 infrared photometer. The entire spectrum of the sample from 600 cm ^-1 to 4000 cm ^-1 is recorded, and the monomer weight% ethylene can be calculated according to the following formula: ethylene weight% = 82.585-111.987X + 30.045 X ² , where X Is the ratio of the higher peak of 1155 cm ⁻¹ and 722 cm ⁻¹ or 732 cm ⁻¹ , whichever is higher.

Preferred semi-amorphous polymers with 10 to 25% by weight of comonomer useful in the present invention have a crystallinity percentage of 2.5 to 25%, preferably 5 to 23%, preferably 5 to 20%. The% crystallinity is determined according to the DSC procedure described above.

Preferred semi-amorphous polymers useful in the present invention are preferably 0.1 to 200 dg / min, preferably 0.1 to 100 dg / min, preferably 0.5 to 50 dg / min, preferably 1 to 25 dg / min, preferably 1 to It should have 20dg / min (measured at ASTM 1238, 2.16 kg and 230 ° C).

Preferred semi-amorphous polymers useful in the present invention preferably have a DSC melting point (Tm) measured according to the DSC procedure described above of 105 ° C. or less, preferably 90 ° C. or less, preferably between 25 and 90 ° C., preferably May be between 30 and 80 ° C, preferably between 35 and 75 ° C.

Preferred semi-amorphous polymers useful in the present invention are based on the weight of the polymer separated as one or two adjacent, soluble moieties, preferably 75% or more of the intermolecular composition distribution, Preferably, it is 80% or more, preferably 85% or more, preferably 90% or more, and the polymer other than the separated polymer is a portion that directly follows before and after the separated polymer. The difference in weight percent of comonomer content in each of these parts does not exceed 20% by weight (relative comparison), preferably not more than 10% by weight (relative comparison) of the average weight percent of comonomer in the copolymer. good. These parts are obtained by raising the temperature by about 8 ° C. during each stage. The intermolecular composition distribution of the copolymer is determined by thermal fractionation in hexene as follows: about 30 g of semi-amorphous polymer is about 1/8 inch (0.32 cm) on that side. ) And is placed in a thick glass jar with a screwed lid with 50 mg of commercially available Ciba-Geigy Corporation antioxidant, Irganoxl076. 425 ml of hexane (the main mixture of normal and iso isomers) is added to the contents of the bottle and the sealed bottle is kept at 23 ° C. for 24 hours. At the end of this time, the solution is transferred to another container and the residue is further treated with hexane at 23 ° C. for a further 24 hours. At the end of this time, the two hexane solutions are combined and evaporated to give a polymer residue that dissolves at 23 ° C. Sufficient hexane is added to the residue to a total volume of 425 ml, and the bottle is immersed in a covered circulating water bath and placed at 31 ° C. for an additional 24 hours. The soluble polymer is transferred to another container and further hexane is added and placed at 31 ° C. for an additional 24 hours before being transferred to the other container. In this way, portions of the semi-amorphous polymer that are soluble at 40 ° C., 48 ° C., 55 ° C., and 62 ° C. are obtained by raising the temperature of about 8 ° C. between each stage. The solutionable polymer is dried, weighed and analyzed for composition as a weight percent of its ethylene content. In order to produce a copolymer with the desired narrow composition, a single site metallocene catalyst is used if (1) only the single statistical mode of the added first and second monomer sequences can be added. (2) It is beneficial if the copolymer is well mixed in a continuous flow stirred tank polymerization reactor that provides only a single polymerization environment for substantially all polymer chains of the copolymer.

Preferred semi-amorphous polymers useful in the present invention preferably have a molecular weight distribution (Mw / Mn) not exceeding 5, preferably 1.5 to 4, preferably 1.5 to 3.

In other embodiments, polymers useful as semi-amorphous polymers in the present invention include heat of fusion of less than 70 J / g, 50 dg / min as determined by Differential Scanning Calorimetry (DSC). The following propylene homopolymers and random copolymers having MFR and having stereoregularity, preferably propylene crystals having isotactic stereoregularity. In other embodiments, the polymer is a random copolymer of propylene and at least one comonomer selected from ethylene, C ₄ -C ₁₂ alpha olefins, and combinations thereof. Preferably, the random copolymer of propylene contains 10 to 25% by weight polymerized ethylene units, based on the total weight of the polymer, and has a narrow intermolecular composition distribution (eg, 75% or more due to thermal fractionation); Or melting point (Tm) of 35 ° C. to 80 ° C .; heat of fusion, upper limit is 70 J / g or 25 J / g and lower limit is 1 J / g or 3 J / g; molecular weight distribution (Mw / Mn) should be 1.8 to 4.5; and the melt flow rate should not exceed 40 dg / min or 20 dg / min (230 ° C., 216 kg, measured by ASTM 1238).

As semi-amorphous polymers, particularly preferred polymers useful in the present invention are polymers that have a medium level of crystallinity due to their stereoregular propylene sequence. This polymer has (A) crystallinity interrupted in a manner such as, for example, regio-inversion and steric defects; (B) propylene crystallinity is at least partially interrupted by comonomers. Or a combination of (C) (A) and (B).

In certain embodiments, the useful polymers described above further comprise non-conjugated diene monomers that assist in later chemical modification of the blend composition (eg, cross-linking). The amount of diene present in the polymer is preferably less than 10% by weight, more preferably less than 5% by weight. The diene can be any non-conjugated diene commonly used in ethylene propylene copolymers, including but not limited to ethylidene norbornene, vinyl norbornene, and dicyclopentadiene.

In some embodiments, the semi-amorphous polymer is a random propylene copolymer with a narrow composition distribution. In another embodiment, the semi-amorphous polymer is a random propylene copolymer having a narrow composition distribution and a melting point of 25 ° C to 120 ° C, preferably a melting point of 25 ° C to 90 ° C. The copolymer is referred to as random because it contains propylene, comonomer and optionally diene and the number and distribution of comonomer residues does not match the statistical random copolymerization of the monomers. In a three-dimensional block structure, the number of block monomer residues of any kind adjacent to each other is higher than expected from the statistical distribution in a random copolymer of similar composition. Ethylene propylene copolymers with historical steric block structures have an ethylene residue distribution that matches these block structures rather than a statistical random distribution of monomer residues in the polymer. Intermolecular composition distribution of the copolymer (i.e., randomness) may be determined by ¹³ C NMR, ¹³ C NMR locates the comonomer residues in relation to nearby propylene residues. The intermolecular composition distribution of the copolymer is determined by thermal fractionation in hexane as already mentioned.

In other embodiments, the semi-amorphous polymer useful in the present invention has a heat of fusion of 70 J / g or less, preferably from 1 to 65 J / g, preferably from 2 as determined by DSC as described above. It should have a heat of fusion of 50 J / g, preferably 4 to 50 J / g.

In other embodiments, the semi-amorphous polymer useful in the present invention has a weight average molecular weight of 20,000 to 1,000,000 g / mol, preferably 50,000 to 500,000 g / mol, preferably 125,000 to 400,000 g / mol. It should have an average molecular weight.

Preferred semi-amorphous polymers used in embodiments of the present invention have a propylene stereoregularity index (m / r) with a lower limit of 4 or 6 and an upper limit of about 8, 10 or 12. The propylene stereoregularity index represented herein by “m / r” is determined by ¹³ C nuclear magnetic resonance (NMR). The propylene stereoregularity index (m / r) is calculated by the method specified in HN Cheng, Macromolecules, 17, 1950 (1984). “M” or “r” represents the stereochemical configuration of a pair of consecutive propylene groups, “m” means meso, and “r” means racemic.

An m / r ratio of 0 to less than 1.0 usually indicates a syndiotactic polymer, an m / r ratio of 1.0 indicates an attack material, and an m / r ratio of greater than 1.0 indicates an isotactic material. The ratio of isotactic materials theoretically approaches infinity and many by-product attack polymers contain sufficient isotactic content, so the ratio is greater than 50.

In certain preferred embodiments, preferred semi-amorphous polymers have propylene crystals with isotactic stereoregularity. As used herein, the term “stereoregular” refers to the overwhelming number in polypropylene, ie, more than 80% of the propylene residues except for other monomers such as ethylene. , 2 insertions and the stereochemical orientation of the pendant methyl group is the same, ie, meso or racemic.

プロピレンコポリマーの¹³CNMRスペクトルは、米国特許5,504,172記載されている様に測定される。メチル炭素領域（１００万当り19-23 部分（ppm））に関するスペクトルは第一の領域（21.2-21.9 ppm）、第二の領域（20.3-21.0 ppm）及び第三の領域（19.5-20.3 ppm）に分けることが出来る。スペクトルの各ピークは刊行物Polymer、30巻、（1989）、1350ページの論文を参照して割り当てた。第一の領域では、PPP(mm)で表わされる3つのプロピレン単位鎖中の第二の単位のメチル基が共鳴する。第二の領域では、PPP(mr)で表わされる3つのプロピレン単位鎖中の第二の単位のメチル基が共鳴し、その隣接する単位がプロピレン単位及びエチレン単位であるプロピレン単位のメチル基（PPE-メチル基）が共鳴する（20.7 ppmの近辺で）。第三の領域では、PPP(rr)で表わされる3つのプロピレン単位鎖中の第二の単位のメチル基が共鳴し、その隣接する単位がエチレン単位であるプロピレン単位のメチル基（EPE-メチル基）が共鳴する（19.8 ppmの近辺で）。三つ組み立体規則性の計算は米国特許5,504,172に示す技法に概観される。第二の領域及び第三の領域の全ピーク領域から、プロピレン挿入（2,1及び1 ,3の双方）による誤りによるピーク領域を差し引くことにより、頭から尾の結合よりなる３プロピレン単位鎖（PPP(mr)及びPPP（rr））に基づきピーク領域を得ることができる。この様にして、PPP(mm)、PPP(mr)、及びPPP(rr)のピーク領域を評価することができ、そして頭から尾の結合よりなるプロピレン単位鎖の三つ組み立体規則性を決定することができる。 A preferred semi-amorphous polymer useful in the present invention is a triad of three polypropylene units of 75% or more, or 80% or more, or 82% or more, or 85% or more, or 90% or more as measured by ¹³ C NMR. Has regularity. Polymer triadic regularity refers to the relative stereoregularity of a sequence of three adjacent propylene units, where the chain consists of head-to-tail linkages and is expressed as a binary combination of m and r sequences. In the semi-amorphous polymer of the present invention, it is usually expressed as a ratio of the number of specific stereoregular units to all of the propylene triads in the copolymer. The triadic stereoregularity (mm portion) of the propylene copolymer can be determined from the ¹³ C NMR spectrum of the propylene copolymer and the following formula:

mm part = PPP (mm) / (PPP (mm) + PPP (mr) + PPP (rr))

Here, PPP (mm), PPP (mr), and PPP (rr) indicate peak regions derived from the methyl group of the second unit in the following three propylene unit chains composed of a head-to-tail bond.

The ¹³ C NMR spectrum of the propylene copolymer is measured as described in US Pat. No. 5,504,172. The spectrum for the methyl carbon region (19-23 parts per million (ppm)) is the first region (21.2-21.9 ppm), the second region (20.3-21.0 ppm) and the third region (19.5-20.3 ppm) Can be divided into Each peak of the spectrum was assigned with reference to the publication Polymer, Volume 30, (1989), page 1350. In the first region, the methyl group of the second unit in the three propylene unit chains represented by PPP (mm) resonates. In the second region, the methyl groups of the second units in the three propylene unit chains represented by PPP (mr) resonate, and the methyl groups (PPE) of the propylene units whose adjacent units are propylene units and ethylene units. -Methyl group) resonates (around 20.7 ppm). In the third region, the methyl group of the second unit in the three propylene unit chains represented by PPP (rr) resonates, and the methyl group of the propylene unit whose adjacent unit is an ethylene unit (EPE-methyl group) ) Resonates (around 19.8 ppm). The calculation of triple stereoregularity is outlined in the technique shown in US Pat. No. 5,504,172. By subtracting the peak region due to the error due to propylene insertion (both 2, 1 and 1, 3) from the total peak region of the second region and the third region, 3 propylene unit chains consisting of head-to-tail bonds ( Peak regions can be obtained based on PPP (mr) and PPP (rr). In this way, the peak areas of PPP (mm), PPP (mr), and PPP (rr) can be evaluated, and the ternary stereoregularity of propylene unit chains consisting of head-to-tail bonds is determined. be able to.

In other embodiments, polymers useful as semi-amorphous polymers in the present invention include heat of fusion of less than 70 J / g, 50 dg / min as determined by Differential Scanning Calorimetry (DSC). Propylene crystals having propylene crystals having propylene crystals having isotactic stereoregularity, including homopolymers and random copolymers of propylene having the following MFR, are preferable. In other embodiments, the polymer is a random copolymer of propylene and is at least one comonomer selected from ethylene, C ₄ -C ₁₂ alpha olefins, and combinations thereof. Preferably the random copolymer of propylene contains from 10 to 25% by weight polymerized ethylene units, based on the total weight of the polymer, and has a narrow intermolecular composition distribution (eg 75% or more); from 25 ° C to 120 ° C, or from 35 ° C Melting point (Tm) at 80 ° C .; upper limit of heat of fusion is in the range of 70 J / g or 25 J / g and lower limit is in the range of 1 J / g or 3 J / g; molecular weight distribution (Mw / Mn) from 1.8 4.5; and the melt flow rate should not exceed 40 dg / min or 20 dg / min (230 ° C., 2.16 kg, measured by ASTM 1238).

Preferred polymers useful as semi-amorphous polymers in the present invention are also referred to as “Second Polymer Component (SPC)” as WO 00/69963, WO 00/01766, WO 99/07788, WO 02 / There is a polymer described in detail in 083753 and further described in WO 00/01745 as “Propylene Olefin Copolymer”. All these documents are hereby incorporated by reference.

A preferred semi-amorphous polymer can be produced as follows in a solution process using a metallocene catalyst. In one preferred embodiment, a continuous solution polymerization process is used to produce a copolymer of propylene and 10 to 25 wt% ethylene is converted to a metallocene catalyst, i.e., dimethylanilium tetrakis- (pentafluorophenyl) boric acid. 1,1'-r-bis (4-triethylsilylphenyl) methylene- (cyclopentadienyl) (2,7- jetter tert-butyl-9- using (dimethylaniliniumtetrakis- (pentafluoro-phenyl) borate) as an activator Fluorenyl) hafnium dimethyl (1,1'-r-bis (4-triethylsilylphenyl) methylene- (cyclopentadienyl) (2,7-di-tertiary-butyl-9-fluorenyl) hafnium dimethyl).

Organoaluminum compounds, i.e., tri-n-octylaluminum, may be added as a scavenger to the monomer feed stream prior to introduction into the polymerization process.

A preferred polymer is dimethylsilylbis (indenyl) hafnium dimethyl in combination with dimethylaniliniumtetrakis (pentafluorophenyl) borate.

In other embodiments, dimethylsilyl bis (2-methyl-5-phenylindenyl) zirconium dialkyl (such as methyl) and / or Dimethylsilyl bis (2-methylphenylindenyl) zirconium dialkyl (such as methyl) is an activator (dimethylaniliniumtetrakis (pentafluorophenyl) borate) (pentafiuorophenyl) borate)) and triarylcarbenium ((pentafluorophenyl) borate)).

Preferably, the solution polymerization is carried out using hexane as a solvent in one or optionally two continuous stirred tank reactors connected in series. In addition, toluene may be added to increase the solubility of the cocatalyst. The feed is transferred to the first reactor at a reaction temperature of about 50 to about 220 ° C. Hydrogen gas may also be added to the reactor as a molecular weight modifier. If desired, the polymer product may then be transferred to a second reactor, which is operated at a temperature of about 50 to about 220 ° C. In addition, monomer, solvent, metallocene catalyst, and activator can be added to the second reactor.

Preferred semi-amorphous polymers may also be advantageously produced by a continuous solution polymerization process as described in WO 02/34795, in a single reactor and separated from the alkane solvent by liquid phase separation. Preferred semi-amorphous polymers may also be produced by the polymerization process described on page 6, lines 24 to 57 of EP1 003814 B1.

More detailed guidance on how to make such preferred semi-amorphous polymers is described in WO 02/083754.

A preferred semi-amorphous polymer useful in the present invention is produced using a metallocene catalyst system.

Preferred semi-amorphous polymers include VM (R) 1000, VM (R) 2000 and VM (R) 3000 available from ExxonMobil Chemical Company, Houston, Texas.

Blend Characteristics In certain preferred embodiments, the blends described herein are heterogeneous and are characterized by a fine distribution of uniformly distributed discontinuous phases in the matrix. The size of the discontinuous phase in the product depends on the product composition and the process used to produce the product. For example, in injection molding, stretching is introduced in the flow direction so that the particles in the dispersed phase stretch somewhat. This is observed in FIG. FIG. 2 is an atomic force microscope (AFM) photograph of a heterogeneous (heterogeneous) blend composition containing 20 wt% and 80 wt% propylene homopolymer of a semi-amorphous propylene-ethylene copolymer containing 14.5 wt% ethylene. . In this figure, the flow direction is the vertical direction. The dispersed phase (semi-amorphous propylene-ethylene copolymer) is shown dark in the micrograph and the matrix (polypropylene) is shown in light color. Despite the effect of stretching in the flow direction, FIG. 2 shows large sized dispersed phase particles that typically do not exceed 1 μm (note that the overall size of FIG. 2 is 5 μm × 5 μm). It can be theorized that this feature of fine dispersion helps to obtain good transparency.

In certain preferred embodiments, the blend of semi-crystalline polymer and semi-amorphous polymer is a heterogeneous blend, preferably the semi-crystalline polymer is a continuous phase and the semi-amorphous polymer is a non-continuous phase. Is good.

In other embodiments, depending on the composition, the blend may be two heterogeneous phases, but the two phases may be continuous with one another. In this case, absolutely one component cannot belong to the matrix and the other phase cannot belong to the dispersed phase, but rather both components share the matrix.

In other embodiments, the blend from which the film is produced is non-uniform, with no more than 20% haze (1 mm thick injection molded tip sample) and film tearing in the Elmendorf MD and TD directions. The strength is 45 g / mil or more, and the total energy impact is 3 ft.lb or more (4.0 J or more).

The blends of the present invention can be made using any procedure that produces an intimate mixture of these components. This includes a reactor blend, in which the semicrystalline polypropylene component is polymerized in one reactor (or one stage of one reactor) and the polymerized product is transferred to another reactor or the same reactor. It is transferred to a different stage where polymerization of the semi-amorphous polymer takes place. The final blend product contains an intimate mixture of the two polymer components. Alternatively, blends can be made by mixing semi-crystalline and semi-amorphous polymers after the reactor. For example, these components may be blended by a tumbler, static mixer, batch mixer, extruder, or combinations thereof.

The mixing step may be performed as part of a processing method used, for example, for extrusion in injection molding, machining or manufacturing of goods such as fiber lines.

Similarly, these components are melt-pressed at 180 ° C with a Carver press to a thickness of 0.5 mm (20 mils), the finished slab is wound up, both ends are folded, and the operations of pressing, winding and stacking are repeated 10 times. Can be combined by doing. Internal mixers are particularly important in solution or melt blending. For the Brabender Plastograph, a blend of 180 to 240 ° C. for 1 to 20 minutes was sufficient. Other methods used to mix the ingredients include blending the polymer in a Banbury internal mixer at a temperature above the flux temperature of all ingredients, eg, 180 ° C. for 5 minutes. . Whether or not the polymerization components are thoroughly mixed is indicated by whether or not the dispersion form of the semi-crystalline polymer and the semi-amorphous polymer is uniform. Continuous mixing may also be used. These processes are well known and include short and twin screw extruders, static mixers that mix low viscosity molten polymer streams, impingement mixers, and disperse semicrystalline and semiamorphous polymer components. Of course, other machines and processes designed to be in intimate contact are included.

In certain preferred embodiments, the blend has a dispersion of semi-amorphous polymer of size less than 4 μm in a continuous phase of semi-crystalline polymer, preferably a dispersion of semi-amorphous polymer (also referred to as dispersed particles). ) The size may be 3 μm or less, preferably 2 μm or less, preferably 1 μm or less. (The average size of the dispersion is 4 μm or less because the dispersion is less than 4 μm).

The blends of the present invention preferably have a permanent tension set of 65% or more, preferably 85% or more, preferably 100% or more, preferably 125% or more, preferably 150% or more.

Permanent tensile strain is measured by the following procedure. A hysteresis test is performed on molded samples with the required dumbbell shape (ASTM standard type I bar polypropylene) according to the following test procedure. Sample deformable zone (2.54 cm length) stretched to 200% of original length at a deformation rate of 20 inches / min (51 cm / min) on an Instron (The Instron Corporation, Canton, MA) test machine It is. The sample is then unwound and the machine moves back to the point where the stress is zero. At this point, the machine will have zero new growth. A second cycle of a new 200% extension is started with the specimen still held. Again the machine returns to the point where the stress is zero in the reverse cycle. Each set of cycles is determined for the point where each elongation is zero. Two specimens are tested for each sample. The average set value of the two cycles is taken as the permanent tensile strain.

The blends of the present invention were measured in a 1 mm thick injection molded haze chip sample according to ASTM D 1003, and 2500 ppm bis (3,4 dimethyl) before the blend was molded into 1 mm chips. Haze tested under conditions combined with benzylidene) sorbitol (also known as DMDBS, available from Milliken Chemicals as Millad 3988), preferably 20% Hereinafter, it is preferably 15% or less, preferably 12% or less, preferably 10% or less.

While the blends of the present invention are combined with a fining agent in a blend haze test, the final film of the present invention may or may not contain a fining agent. Film haze is also measured according to ASTM-D 1003.

The blends of the present invention contain less than 5% by weight filler based on the weight of polymer and filler.

In other embodiments, the blends of the present invention preferably have a melt flow rate of 0.1 to 200 dg / min (ASTM D-1238 condition L; 230 ° C., 2.16 kg), preferably 0.1 to 100 dg / min, preferably 0.5 To a melt flow rate of from 0.5 to 30 dg / min, preferably from 0.5 to 30 dg / min, preferably from 0.1 to 25 dg / min.

In other embodiments, the heterogeneous blends of the present invention exhibit a surprisingly good blush resistance (i.e., very low for no stress-whitening). Stress whitening or fog resistance in a heterogeneous propylene copolymer is caused by the formation of voids or fine cracks when a force is applied while the specimen is deformed. Light is diffracted from the cracks and voids and whitening occurs, resulting in an undesirable appearance. A detailed test procedure for quantifying the amount of stress whitening is described below. In short, an impact is given to the molded part using a drop impact tester. If the sample is affected, stress whitening occurs due to the impact of the weight of the punch.

Color readings (hunter color “L”; white-black spectral measurements) are taken on the molded specimen and outside the impact area. The level of stress whitening is determined as the difference between the two measurement Hunter “L” color readings. In other words, ΔL is defined and determined as the hunter “L” value in the impact area minus the hunter “L” value in the non-impact area. In some embodiments, the heterogeneous blends of the present invention exhibit a ΔL of less than 25, preferably less than 20, preferably less than 15, preferably less than 10, preferably less than 5. In other embodiments, the blends of the present invention exhibit a negative ΔL (ie, the impact zone hunter “L” value is less than the non-impact zone hunter “L” value).

Stress Whitening Test Procedure: Injection molded 125 mil (3.18 mm) thick specimen (eg Gardner disk) using a drop tester and weighing 4 pounds (1.82 kg) 5 inches (ie 20 inches. Pounds) Or drop from a height of 2.26J) to give an impact. The strike weight impact is used to cause stress whitening in the specimen if the specimen is affected. After impact, the specimen is aged for 24 hours.

After aging, color readings are taken using the Hunter ColorQuest XE colorimeter and outside the impact area and impact area. A colorimeter is set up for hunter experiment reading using a D65 / 10 ° illuminator. D65 or D ₆₅ represents the daylight to be used most commonly, is a daylight illuminant. 10 indicates an angle cover with a luminous body (for example, 10 degrees). Reading is taken in the impact area of the disc centered on the reflective aperture. Readings are also taken outside the impact area. The level of stress whitening is determined as the difference between the two measured Hunter “L” readings. Hunter “L” is measured by white-black color spectrum (L = 100 white, L = 0 black). If the sample shows stress whitening and the impact zone “L” value is higher (whiter) than the non-impact zone “L” value, then a positive ΔL (impact zone “L” value minus the non-impact zone “L” "Value) is obtained. The ΔL value provides a means for comparing the relative susceptibility to stress whitening in a set of samples. Usually three specimens per sample are tested and the “L” value is averaged.

In certain embodiments, the blends of the present invention may also include a third polymer component. The third polymer component may be added to the semi-crystalline polymer, semi-amorphous polymer or blend by known methods. In these embodiments, the third polymer component (TPC) is low density polyethylene (density 0.915 to 0.935 g / cm ³ ), linear low density polyethylene, ultra low density polyethylene (density 0.85 to 0.90 g / cm ³ ). ³ ), very low density polyethylene (density 0.90 to 0.915 g / cm ³ ), medium to low density polyethylene (density 0.935 to 0.945 g / cm ³ ), high density polyethylene (density 0.945 to 0.98 g / cm ³⁾ Or a combination thereof. For example, polyethylene produced using a metallocene catalyst system (mPE), ie, an ethylene homopolymer or copolymer, may be used. In one characteristic example, mPE homopolymers and copolymers were produced in solution, slurry, high pressure or gas phase, combining mono- or bis-cyclopentadienyl transition metal catalysts with aluminoxanes and / or non-conjugated anions. Sometimes it is a thing. The catalyst and activator may or may not be supported and the cyclopentadienyl ring may be substituted or unsubstituted. Without limitation, the products described herein are trade names of EXCEED® and EXACT®, which are particularly known in the industry from ExxonMobil Chemical Company, Houston, Texas. Available on the market. In other embodiments, the third component is a propylene polymer or copolymer, EP / EPDM copolymer rubber, EVA, or other type of polyolefin.

The blends of the present invention may contain additives and other ingredients. For example, the blends of the present invention may contain slip agents, preferably from 50 ppm to 10% by weight, preferably from 50 to 5000 ppm. Preferably the slip agent is based on the weight of the composition from 0.001 to 1% by weight (10 to 10,000 ppm), more preferably from 0.01 to 0.5% by weight (100 to 5,000 ppm), more preferably from 0.1 to 0.3% by weight (from 1,000 to 3,000 ppm). Desirable slip additives include, but are not limited to, saturated fatty acid amides (eg, palmitamide, stearamide, arachidamide, behenamide, stearyl stearamide, Palmityl palmitamide, and stearyl arachidamide; saturated ethylene-bis-amides (eg, stearamide-ethyl-stearamide, stearamide-ethyl-palmitamide) (stearamido-ethyl-palmitamide), and palmitoamido-ethyl-stearamide; unsaturated fatty acid amides (eg oleamide, erucamide and linoleamide) )); Unsaturated Ethi Unsaturated ethylene-bis-amides (eg, ethylene-bis-stearamide, ethylene-bis-oleamide, stearyl-erucamide, Eramido-ethyl-erucamide, oleamido-ethyl-oleamide, eramido-ethyl-oleamide, oleamido-ethyl-erucamide ), Stearamido-ethyl-erucamide, erucamido-ethyl-palmitamide, and palmitoamido-ethyl-oleamide); glycols; Polyether polyols (eg, Carbowax); acids of aliphatic hydrocarbons (eg, Adipic acid and sebacic acid; esters of aromatic or aliphatic hydrocarbons (eg glycerol monostearate and pentaerythritol monooleate) (Pentaerythritol monooleate)); styrene-alpha-methyl styrene; fluoro-containing polymers (eg, polytetrafluoroethylene, fluorine oils) , And fluorine waxes; silicon compounds (eg, silanes, silicone oils, silicone polymers, modified silicones and curing) Silicones (cured silicones); sodium alkylsulfates , Alkyl phosphoric acid ester (alkyl phosphoric acid esters); including and mixtures thereof. The preferred slip additive is an unsaturated fatty acid amide, available from Crompton (Kekamide® grade) and Croda Universal (Crodamide® grade). Particularly preferred are the unsaturated fatty acid amides erucamide and oleamide. Preferred slip agents include amides having the chemical structure CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) _X CONH ₂ , where x is 5 to 15. A particularly preferred amide is 1) Erucamide CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₁₁ CONH ₂ , also called cis-13-docosenoamide (erucamide is Akzo Available from Nobel Amides Co. Ltd. under the trade name ARMOSLIP E); 2) Oleylamide CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₈ CONH ₂ ); and 3) Oleamide ( Oleamide), which also includes CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) ₇ CONH ₂ , also referred to as N-9-octadecenyl-hexadecanamide. In other embodiments, stearamide is also useful in the present invention. Other preferred slip additives include those described in WO 2004/005601 Al.

The blends of the present invention may also contain a clarifying agent. Preferably, the fining agent is present from 10 ppm to 10 wt%, more preferably from 25 ppm to 5 wt%, preferably from 50 ppm to 4000 ppm, based on the weight of the total polymer in the blend composition. Preferred fining agents include organic phosphoric acid, phosphate esters, sodium benzoate, talc, sorbitol, adipic acid, benzoic acid (or metal salts of these acids), inorganic fillers, and the like. Preferred fining agents preferably include agents based on 50 to 4000 ppm sorbitol, aluminum salt based agents and sodium salt based agents. Preferred fining agents include nucleating agents such as Hyperform (eg HPN-68) and Millad additives from Milliken Chemicals, Spartanburg, SC (eg Millad 3988-3,4-dimethylbenzylidene sorbitol, dibenzylidene sorbitol (Millad 3988- 3,4-dimethylbenzylidene sorbitol, dibenzylidene sorbitol) and organophosphates such as Am-11 Chemicals, Allendale, NJ NA-11 and NA-21.

Other nucleating agents, such as Ziegler-Natta olefin products or other highly crystalline polymers can also be used. Particularly preferred fining agents are disodium [2.2.1] heptane bicyclodicarboxylate, bis (3, 4 dimethylbenzylidene) sorbitol, sodium 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate, (p-chloro , P'methyl) dibenzylidene) sorbitol (bis (p-ethylbenzylidene sorbitol), 1,2,3,4-dibenzylidene sorbitol (bis (p-ethylbenzylidene sorbitol)) 1,2,3,4-dibenzylidene sorbitol), 1,2,3,4-di-para-methylbenzylidene sorbitol, and / or aluminum 2, 2'-methylene-bis (4,6-di-butylphenyl) phosphate (aluminum 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate).

In addition, various additives may be incorporated in the above embodiments to make blends and films for various purposes. Such additives include, for example, stabilizers, antioxidants, fillers, colorants, and antiblock agents. Primary and secondary antioxidants include, for example, hindered phenols, hindered amines, and phosphites. Nucleating agents include, for example, sodium benzoate and talc. Other nucleating agents may also be Ziegler / Natta olefin products or other highly crystalline polymers. Anti-tacking agents include amorphous silica, talc, especially zinc stearate. Additives such as dispersants can also include, for example, Acrowax C. Catalyst deactivators are also commonly used, such as calcium stearate, hydrotalcite and calcium oxide and / or other acid neutralizers known in the art.

Other additives include, for example, flame retardants, plasticizers, sulfurizing agents or curing agents, sulfurization accelerators, or curing accelerators, curing inhibitors, processing aids, adhesive resins, and the like. Such additives also include fillers and / or reinforcements, which may be added independently or incorporated into the additive. Examples of these include graphite, clay, talc, calcium carbonate, mica, silica, silicates, combinations thereof, and the like. Other additives used to improve properties include lubricants and UV stabilizers. What is listed herein does not include all types of additives used in the present invention. From these disclosures, those skilled in the art will be able to mention other additives to improve the properties. As will be appreciated by those skilled in the art, the blends of the present invention can be modified to suit the desired blend characteristics.

Process oil can also optionally be added in the embodiments described above. The blend may include process oil in the range of 1 to 50, alternatively 2 to 20 parts by weight of process oil per 100 parts of the total polymer component. Add moderate amounts of process oil to reduce the viscosity and stiffness of the blend while improving the properties of the blend near and below 0 ° C. These benefits arise from lowering the Tg of the blend. Other benefits of adding process oil to the blend include improved processability and improved balance between elasticity and tensile strength. Process oils typically contain (a) hydrocarbons consisting essentially of carbon and hydrogen with few heteroatoms such as oxygen, or (b) essential such as dioctyl phthalate, ethers and polyethers. Consisting of carbon, hydrogen and at least one heteroatom. Preferred process oils have a high boiling point that substantially volatilizes at 200 ° C.

Such process oils are usually obtained as a free flowing powder as a pure solid, or as a pure liquid, or as a mixture of these materials physically absorbed on an inert carrier (eg, clay, silica). Other useful process oils include a mixture of many compounds consisting of linear and acyclic but branched, cyclic and aromatic carbonaceous structures. Another family of useful process oils are certain low to medium molecular weight (molecular weight (Mn) <10,000) organic esters and alkyl ether esters. Examples of process oils include The Sun Manufacturing Company of Marcus Hook, PA, USA Sunpar® 150 and 220, and Ergon, Jackson, Mississippi Hyprene® V750 and Hyprene® V1200, and There is IRM 903 at Calumet Lubricants Company, Princeton, Louisiana. It is anticipated that combinations of the process oils described above may also be implemented in the present invention. Two-phase blends and multi-phase blends may also be considered, but in one embodiment, in each process oil selection, the process oil is compatible or miscible with the blend composition in the melt and has a uniform consistency. It is important that they form a blend of phases.

The process oil may be added to the blend or blend polymer composition by any method known in the art.

The addition of certain process oils to lower the glass transition temperature of isotactic polypropylene and ethylene propylene diene rubber blends is described by Ellul in US Pat. Nos. 5,290,886 and 5,397,832. These procedures can be easily applied to the present invention.

In certain embodiments, the components along with the blend may include various amounts of plasticizer. In some embodiments, the plasticizer comprises C ₆ to C ₂₀₀ paraffins, and in other embodiments C ₈ to C ₁₀₀ paraffins. In another embodiment, the plasticizer consists paraffins C ₂₀₀ from a substantially C _6, also consisting of paraffins C ₁₀₀ from substantially C _8. In relation to the purpose of the invention and in the description herein, “paraffins” includes all isomers such as n-paraffins, branched paraffins, isoparaffins, and cycloaliphatics, and blends thereof. It may be included, synthesized by methods known in the art, or derived from refining from crude oil. Suitable plasticizers also include "isoparaffins", "polyalphaolefins (PAO)" and "polybutenes" (a subgroup of PAO). These three classes of compounds can also be represented as paraffins, which may include branched, cyclic, and normal structures and blends thereof. In some embodiments, these may include C ₆ to C ₂₀₀ paraffins, and in other embodiments, may include C ₈ to C ₁₀₀ paraffins. Preferred plasticizers include those described in WO 2004/014998 (this document is incorporated herein by reference), in particular the plasticizers described on page 9, line 31 to page 26, line 19. Preferred polyalphaolefins (PAO) useful in the present invention include those described in WO 2004/014998, in particular the plasticizers described on page 17, line 19 to page 19, line 25. Likewise preferred Group III Basestocks may be used as the plasticizer of the present invention. Preferred group III base stocks are those described in WO 2004/014998, particularly hydrotreated under severe conditions, with a saturation level of 90% or more, preferably 92% or more, preferably 94% or more, or preferably 95 Mineral oil having a viscosity index (VI) of more than 120, preferably 130 or more, with a sulfur content of less than 0.03%, preferably between 0.001 and 0.01%. Preferably the Group III hydrocarbon base stock has a kinematic viscosity at 100 ° C. of 3 to 100 cSt, preferably 4 to 100 cSt, preferably 6 to 50 cSt, preferably 8 to 20 cSt; and / or a number average molecular weight of 300 5000, preferably 400 to 2,000, more preferably 500 to 1,000; and / or carbon numbers 20 to 400, preferably 25 to 400, preferably 35 to 150, more preferably 40 to 100. The plasticizer is in one embodiment 0.1 to 60% by weight in each of the blends of the invention (each based on the weight of the blend), in other embodiments 0.5 to 40% by weight, yet another embodiment. 1 to 20% by weight, and in still other embodiments 2 to 10% by weight. Here, the desirable range includes a combination of any weight% of the upper limit numerical values described above and any weight% of the lower limit numerical values.

Film In one embodiment, the blend of the present invention is formed into a film. Polyolefin films are widely used, for example, for shopping bags, pressure-sensitive adhesive tapes, gift packaging, labels, food packaging, non-food packaging, and medical applications. These applications require high tear strength (machine direction and transverse direction) and impact force, fracture resistance, high gloss, and low haze. The blends described above can be formed into single or multilayer films suitable for their application. These films can be formed by any conventional technique known in the art, including extrusion, coextrusion, extrusion coating, lamination, blowing and casting. The film can be formed by a flat film or a tube forming process and subsequently stretched uniaxially or biaxially perpendicular to each other in the film plane. One or more layers of the film may be stretched to the same or different extent in the transverse direction and / or longitudinal direction. This stretching may be performed before or after each individual layer is united. For example, the polyethylene layer can be extrusion coated or laminated onto stretched polypropylene, or the polyethylene and polypropylene can be coextruded together into a film and then stretched. Similarly stretched polypropylene can be laminated to stretched polyethylene, or the stretched polyethylene can be coated onto polypropylene, and optionally this combination can be further stretched. Usually, the film is stretched at a rate of up to 15, preferably 5 to 7 in the machine direction (MD) and up to 15, preferably 5 to 9 in the transverse direction (TD).

However, in other embodiments, the film is stretched to the same extent in both MD and TD directions.

In other embodiments, the layers comprising the blends described herein may be combined with one or more other layers. The other layer (s) can be any layer typically included in a multilayer film structure. For example, the other single layer or layers may be:

1. Polyolefins Preferred polyolefins include homopolymers or copolymers of C ₂ to C ₄₀ olefins, preferably C ₂ to C ₂₀ olefins, preferably alpha and other olefin copolymers, or alpha olefins (ethylene is the object of the present invention). It is better to be defined as alpha olefin). Preference is given to homopolyethylene, homopolypropylene, propylene copolymerized with ethylene and / or butene, ethylene copolymerized with one or more propylene, butene or hexene and an optional diene. Preferred examples include very low density polyethylene, very low density polyethylene, linear low density polyethylene, low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic. Rick polypropylene, propylene and ethylene and / or butene and / or hexene random copolymers, ethylene propylene rubber, ethylene propylene diene monomer rubber, elastomers such as neoprene, and thermoplastic polymers such as, for example, thermoplastic elastomers and rubber reinforced plastics And blends of elastomers.

2. Polar Polymers Preferred polar polymers include ethylene with one or more polar monomers such as esters, amides, acetates, anhydride homopolymers and copolymers, acetates, anhydrides, esters, alcohols, and / or acrylic resins and And / or copolymers of C ₂ to C ₂₀ olefins such as propylene and / or butene. Preferred examples include polyester, polyamide, ethylene vinyl acetate copolymer, and polyvinyl chloride.

3. Cationic Polymers Preferred cationic polymers include pairs or disubstituted olefins, alpha-heteroatom olefins and / or polymers or copolymers of styrene monomers. Preferred paired disubstituted olefins include isobutylene, isopentene, isoheptene, isohexene, isooctene, isodecene and isododecene.

Preferred alpha heteroatom olefins include vinyl ether and vinyl carbazole, and preferred styrene monomers include styrene, alkyl styrene, paraalkyl styrene, alphamethyl styrene, chlorostyrene and bromo-para-methyl styrene. Examples of preferred cationic polymers include isobutylene copolymerized with butyl rubber, paramethylstyrene, polystyrene, and polyalphamethylstyrene.

4). Other preferred layers are paper, wood, cardboard, metal, metal foil (aluminum foil and tin foil), vapor deposition surface, glass (including silicon oxide (SiO.x) film with silicon oxide deposited on the film surface) Woven fabrics, spunbond fibers and fabrics, and nonwoven fabrics (particularly polypropylene spunbonded fibers and fabrics or nonwoven fabrics) and substrates coated with inks, pigments, pigments, and the like.

The thickness of the film varies depending on the application purpose, but a film having a thickness of 1 to 250 μm is usually suitable. The packaging film is usually 1 to 250 μm thick. The thickness of the sealing layer is typically 0.2 to 50 μm. There may be a seal layer on both the inner and outer sides of the film, or the sealing layer may be on either the inner or outer side only.

Additives such as slips, anti-blocking agents, antioxidants, pigments, fillers, processing aids, UV stabilizers, neutralizing agents, lubricants, surfactants and / or nucleating agents may be one or more of the film May be present in any layer. Examples of useful additives include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, pigments, waxes, calcium stearate, graphite, low molecular weight resins and glass beads.

In other embodiments, one or more layers may be modified by corona treatment, electron beam irradiation, gamma irradiation, microwave irradiation or metallizing. In certain preferred embodiments, one or two surface layers are modified by corona treatment.

The films described herein may also contain 5 to 60% by weight hydrocarbon resin, based on the weight of the polymer and resin. The resin may be combined with a polymer sealing layer or may be combined with the polymer in the core layer. The resin preferably has a softening point above about 100 ° C., more preferably from 130 to 180 ° C. The film containing a hydrocarbon resin may be stretched to the same or different extent in a uniaxial or biaxial direction.

In certain preferred embodiments, the present invention relates to a film comprising a layer comprising one or more blends as described above, wherein the layer is 2.5 to 635 μm / 0.1 to 25 mils thick, the film comprising:
Haze is less than 10%,
1 degree secant tensile modulus (1 ° Secant Tensile Modulus) is 100,000 to 30,000 psi (690 to 207 MPa),
Elmendorf tear strength in both machine direction and transverse direction is 45 g / mil or more (1.77 g / μ or more),
The total energy impact is 4 J or more, and the melt flow rate is 0.1 to 100 dg / min.

In certain preferred embodiments, the films and / or layers comprising the blends described herein are 2.5 to 635 microns (μm) thick, preferably 5 to 550 μm thick, preferably 10 to 500 μm thick. Preferably, it has a thickness of 25 to 400 μm, preferably 20 to 200 μm.

The film of the present invention has a haze measured by ASTM D 1003 of preferably 10% or less, preferably 5% or less, preferably 3% or less, preferably 2% or less, preferably 1% or less, preferably Is better than 0.5%.

In other embodiments, unless otherwise specified, the films of the present invention preferably have a 45 degree gloss (MT and TD) measured by ASTM D 2457 at a 45 degree angle of 70 or more, preferably 75 or more, preferably 80 or more, preferably 82 or more, preferably 85 or more, preferably 90 or more.

In another embodiment, the film of the present invention has a low modulus (high level of softness); preferably a 1 ° secant Tensile Modulus (measured by ASTM D882) of 125,000 to 100,000 psi ( 690 to 860MPa), 125,000 to 50,000psi (345 to 860MPa), 125,000 to 30,000psi (205 to 860MPa).

In other embodiments, the films of the present invention preferably have a machine direction Elmendorf tear strength of 45 g / mil or greater (1.77 g / μ or greater), preferably 45 g / μm, as measured by ASTM D1922. Mill to 75 g / mil (1.77 g / μ to 2.95 g / μ), preferably 45 g / mil to 100 g / mil (1.77 g / μ to 3.94 g / μ), preferably 45 g / mil to 120 g / mil (1.77 g) / μ to 4.72 g / μ), and the average film thickness should be standardized to a mil (0.001 inch or 25.4 / μm).

In another embodiment, the film of the present invention preferably has a total impact energy (ASTM D 4272-99) of 3 ft.lb or more (4 J or more), preferably 2 to 6 ft.lb (2.7 to 8.1 J). Is good.

In other embodiments, the film of the present invention preferably has an ultimate tensile strength (measured by ASTM D882) of 6,000 psi or more (41.4 MPa) in both the MD and TD directions.

In another embodiment, the film of the present invention may have an elongation at break (measured by ASTM D882) of at least 600% in both the MD and TD directions.

In another embodiment, the film of the present invention preferably has a puncture energy (Puncture Energy) measured by ASTM D5748-95 of preferably 25 in. 1b / mil (0.11 J / μm) or more. However, i) Use a 0.75-inch diameter matte stretch stainless steel deep needle instead of a 0.75-inch diameter pear-shaped TFE fluorocarbon-coated deep needle (probe), and ii) Weigh separately for each test specimen Instead, the average of the measured values of all test specimens was used.

In other embodiments, the films of the present invention preferably have a fracture resistance, as measured by ASTM D 5748-95, of preferably 8 lb / mil (1.4 N / μm) or greater. However, the measurement method change described above was adopted.

The blends of the present invention can be used in applications requiring soft films such as those used in diapers. It is widely used in packaging films because of its high tear resistance and total energy impact resistance and low haze.

In a further embodiment, the present invention relates to:
1. A film containing a heterogeneous blend, which blend:
1) 60 to 99% by weight of one or more semi-crystalline polymers (based on the weight of semi-crystalline and semi-amorphous polymers), each semi-crystalline polymer being propylene and 0 to 5% by weight alpha olefin Comonomer (based on the weight of the polymer), each of the semi-crystalline polymers having a melting point of 100 to 170 ° C. and a melt flow rate of 200 dg / min or less; Comprising a crystalline polymer (based on the weight of semi-crystalline and semi-amorphous polymer), each semi-amorphous polymer being propylene and 10 to 25% by weight of one or more C2 and / or C4 to C10 alpha olefin comonomers Each of the semi-amorphous polymers includes:
a) heat of fusion from 4 to 70 J / g,
b) Melt flow rate from 0.1 to 200 dg / min,
c) The intermolecular composition distribution determined by thermal fractionation in hexane is separated by more than 85% of the polymer weight as one or two adjacent soluble parts and the rest of the polymer Are directly preceding or succeeding parts; each of these parts has a weight percent comonomer content in a range not exceeding 20 weight percent compared to the average weight percent copolymer comonomer content;
d) 1.5 to 4 Mw / Mn,
e) propylene triad stereoregularity measured by ^l3 C NMR, is 75% or more,
The blend is:
i) a melt flow rate of 0.5 to 100 dg / min, and
ii) 0 to 5 wt% filler based on the weight of polymer and filler, and
iii) has a haze of 20% or less measured with a 1 mm thick injection molded chip,
iv) the permanent set is greater than 65%; and the film is 0.1 to 25 mils (2.5 to 635 microns) thick, and
Less than 10% haze,
1-degree secant tensile modulus is 100,000 to 30,000 psi,
Elmendorf tear strength in the machine direction is over 45g / mil,
Elmendorf tear strength in the transverse direction is over 45g / mil,
Total impact energy is 3J or more, and
45 degree gloss is 82 or more,
With the characteristics of

2. In the film of paragraph 1, the semicrystalline polymer comprises propylene and 1 to 3% by weight of C ₂ to C ₁₀ alpha olefin comonomer.

3. In the film of paragraph 2, the alpha olefin comonomer is selected from the group consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, and decene.

4). In the film of paragraph 2, the alpha olefin comonomer is selected from the group consisting of ethylene, butene, hexene and octene.

5. In the film of paragraph 2, the alpha olefin comonomer is ethylene.

6). In the film of paragraph 1, the semicrystalline polymer contains 0% by weight comonomer.

7. In any of the paragraphs above, the semicrystalline polymer has a melting point of 120-170 ° C.

8). In any of the above paragraphs, the semicrystalline polymer has a Mw / Mn of 1.5 to 4.

9. In any of the above paragraph films, the semi-amorphous polymer comprises propylene and 10 to 20% by weight of a C ₂ to C ₁₀ alpha olefin comonomer.

10. In the film of paragraph 9, the alpha olefin comonomer is selected from the group consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, and decene.

11. In the film of paragraph 9, the alpha olefin comonomer is selected from the group consisting of ethylene, butene, hexene, and octene.

12 In the film of paragraph 9, the alpha olefin comonomer is ethylene.

13. In any paragraph film above, the semi-amorphous polymer has a percent crystallinity of 2 to 25%.

14 In any of the paragraphs above, the semi-amorphous polymer has a melt flow rate of 0.1 to 25 dg / min.

15. In any of the paragraphs above, the semi-amorphous polymer has a melting point of 30 to 80 ° C.

16. In any of the above paragraphs, the semi-amorphous polymer has a stereoregularity index of 4 to 12.

17. In any of the above paragraphs, the semi-amorphous polymer should have a propylene triad stereoregularity of 80% or more, preferably 85% or more, preferably 90% or more.

18. In any of the above paragraphs, the blend should have a haze of 15% or less, preferably 12% or less, preferably 10% or less.

19. In any of the above paragraphs, the film should have a gloss of 85 units or more, preferably 89 or more, preferably 90 or more.

20. In any paragraph film above, the semi-amorphous polymer contains 11 to 25% by weight comonomer and is present at 15 to 40% by weight, and the blend is less than 4 μm in the continuous phase of the semi-crystalline polymer. Size semi-amorphous polymer dispersion, and the film has an Elmendorf tear strength in the machine direction of 60 g / mil (2.4 g / μm) or more, haze of 2% or less, 45 degree gloss of 87 units or more The first-degree secant tensile modulus is 75,000 psi (517 MPa) or less, and the total energy impact is 3 J or more.

21. In the films of paragraphs 1 to 19, the semi-amorphous polymer contains 11 to 25% by weight of comonomer and is present in 25 to 40% by weight, and the blend is less than 4 μm in size in the continuous phase of the semi-crystalline polymer. With a semi-amorphous polymer dispersion, and the film has an Elmendorf tear strength in the machine direction of 100 g / mil (2.4 g / μm) or more, a haze of 1.5% or less, a 45 degree gloss of 88 units or more, The 1-degree secant modulus is 50,000 psi (517 MPa) or less, and the total energy impact is 7 J or more.

22. In any of the above paragraphs, the blend should have a permanent set of 165% or more, preferably 175% or more, preferably 200% or more.

23. In any of the above paragraphs, the blended 3.18 mm thick injection molded pad has a resistance ΔL to hunter stress whitening of 20 or less, preferably 15 or less, preferably 10 or less, preferably 5 or less. good.

24. In any of the above paragraphs, the film should have a haze of 4% or less, preferably 3% or less, preferably 2% or less.

25. In the film of paragraph 23, the film has a haze of 5% or less, an MD Elmendorf tear strength of 50 g / mil or more, and a total energy impact of 3 J or more.

26. For the film of paragraph 23, the haze of the film is 2% or less, the MD Elmendorf tear strength is 100 g / mil or more, and the total energy impact is 7 J or more.

27. The film in any of the above paragraphs is a film:
a) Has a haze of 2% or less,
b) Tensile strength at break in the machine direction is greater than 40 MPa,
c) The tensile strength at break in the transverse direction is greater than 40 MPa,
d) The elongation at break in the machine direction is greater than 500%,
e) Elongation at break in the transverse direction is greater than 500%,
f) Elmendorf tear strength in the machine direction is 50 to 150 g / mil,
g) The transverse Elmendorf tear strength is 100 to 400 g / mil
h) fracture resistance of 6 to 10 lb / mil, and
i) The tensile modulus in the machine direction is less than 350 MPa28. In any of the above paragraphs, the film is a cast film, blow molded film or laminated film.

29. In any of the above paragraphs, the film is coextruded or laminated.

30. In any of the above paragraphs, the film has two or more layers.

31. In any of the paragraphs above, the film includes a core layer that includes a heterogeneous blend.

32. In any of the above paragraphs, the film comprises a skin layer comprising a heterogeneous blend.

33. In any of the above paragraph films, the blend of semi-crystalline polymer and semi-amorphous polymer may further comprise a plasticizer, preferably a polyalphaolefin, preferably polydecene.

34. In any of the paragraphs above, the heterogeneous blend should further contain a slip agent, preferably 50 to 5000 ppm amide having the chemical formula CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) _X CONH _2. , Where x is 5 to 15.

35. In any of the above paragraphs, the heterogeneous blend further includes a fining agent, preferably the fining agent is 10 ppm to 10 wt% (more preferably 25 ppm to 5 wt%, based on the total polymer in the blend composition, more Preferably 50 ppm to 4000 ppm) containing organic phosphoric acid, phosphate ester, sodium benzoate, talc, sorbitol, adipic acid, benzoic acid (or metal salts of these acids), inorganic fillers, preferred clarifiers are sorbitol Based agents, aluminum salt-based agents or sodium salt-based agents, Ziegler Nutter olefin products or other highly crystalline polymers, the preferred fining agent being disodium [2.2.1] Heptane bicyclocarboxylate (bis (3, 4 dimethylben), bis (3,4 dimethylbenzylidene sorbitol) zylidene) sorbitol), sodium 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate ), (P-chloro, p'methyl), dibenzylidene sorbitol, bis (p-ethylbenzylidene sorbitol, 1,2, 1,4-3,4-dibenzylidene sorbitol (1,2,3,4-dibenzylidene sorbitol), 1,2,3,4-di-para-methylbenzylidene sorbitol ), And / or aluminum 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate (aluminum 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate It is.

36. In the films of paragraphs 1 to 35, the semi-amorphous polymer has an intermolecular composition distribution of 85% or more, preferably 90% or more by weight of the polymer separated as one or two adjacent soluble parts. The remaining portion of the polymer is the portion that immediately precedes or follows it, and each of these portions is 20% (relatively), preferably more than 10% by weight of the average weight percent of the comonomers of the copolymer Contains no range of weight percent comonomer.

37. In any of the above paragraph films, the blend is such that the semi-amorphous polymer is dispersed in a continuous layer of semi-crystalline polymer with a size less than 4 μm, preferably less than 3 μm, preferably more than 2 μm. It is good that the particles are dispersed in a small size, preferably a size smaller than 1 μm.

38. In any of the above paragraphs, the film has a haze of 1% or less.

39. In any of the above paragraphs, the film is laminated to a substrate, which is preferably a nonwoven, paper, polyolefin, wood, cardboard, metal, metal foil, vapor deposition surface, glass and / or glass coating. Is good.

40. In any of the above paragraphs, the film is laminated to a substrate, and the substrate is coated with ink, dye and / or pigment.

41. Packaging containing the film of any of the above paragraphs.

42. Diapers, medical films, or packaging films, including the film of paragraphs 1-40.

Example
Mw, Mn, Mz were measured by gel permeation chromatography (Gel Permeation Chromatography) as described above.

Mooney viscosity is measured according to ASTM D 1646.

Melt flow rate (MFR) was measured at 230 ° C. under a load of 2.16 kg under ASTM D 1238 Condition L.

The weight percent of ethylene was measured as follows. A thin uniform film was pressed at temperatures above about 150 ° C. and placed in a Perkin Elmer PE 1760 infrared spocnophotometer. A full spectrum of a sample from 600 cm ^-1 to 4000 cm ^-1 was recorded and the ethylene monomer weight percent was calculated according to the following formula: ethylene weight percent = 82.585 −111.987X + 30.045X ² , where X is 1155 cm ^-1 peak height and the ratio of the higher peak height of 722 cm ^-1 or 732 cm ^-1 , whichever is higher.

Glass transition temperature (Tg), β relaxation, loss modulus (Loss Modulus E ") and storage modulus (Storage Modulus (E ')) are dynamic mechanical thermal analysis (DMTA). The instrument used was an RSA II, Rheometries Solid Analyzer II from TA Instruments, New Castle, DE The instrument was operated in tension mode and a molded rectangular sample was used. .

Sample conditions were: 0.1% elongation, 1 HZ frequency and 2 ° C. heating per minute, temperature range from −135 ° C. to sample melting point.

Samples were molded at about 200 ° C. The dimensions vary from sample to sample, but a typical sample was 23 mm long x 6.4 mm wide x (thickness between 0.25 mm and 0.7 mm). tan δ is a ratio of E ″ / E ′, E ′ is a storage modulus (Storage Modulus), and E ″ is a loss modulus (Loss Modulus). The results of these DMTA experiments show that the storage modulus E 'is the loss modulus E ".

Storage modulus measures the material's elastic response or ability to store energy, and loss modulus measures the material's viscous response or ability to diverge energy. The ratio of E ″ / E ′ (= tanδ) is a measure of the damping ability of the material. The mechanism of energy dissipation (ie, relaxation mode) appears as a peak at tanδ, with E ′ as a function of temperature. The uncertainty associated with the reported E 'value is due to variables occurring in the molding process and is expected to be at a level of ± 10%.

Crystallization temperature (Tc), melting point (Tm) and heat of fusion (Hf, ΔH, or ΔH _f ) were measured using a differential scanning calorimeter (DSC). This analysis was performed using TA Instruments MDSC 2920 or Perkin Elmer DSC7. Typically, 6 to 10 mg of molded or plasticized polymer was enclosed in an aluminum pan and inserted into the device at room temperature. Melting data (first heating) was obtained by heating the sample to a temperature at least 30 ° C. above the melting point at a rate of 10 ° C./min. This gives information about the melting behavior under the as-molded condition, which behavior can be influenced not only by the molded orientation or stress, but also by the thermal history. The sample was then placed at this temperature for 10 minutes to destroy its thermal history. Crystallization data was obtained by cooling from the melting point to a temperature at least 50 ° C. below the crystallization temperature at a cooling rate of 10 ° C./min. Typically, the blend sample was cooled to -25 ° C. The sample was placed at this temperature for 10 minutes and finally heated at 10 ° C./minute to obtain further melting data (second heat). The melting points described in the table are peak melting points in the second heating unless otherwise specified. For polymers showing multiple peaks, high melting peak temperatures have been reported. The area under the curve was used to determine the heat of fusion (ΔH _f ) from which the degree of crystallization can be calculated. A value of 189 J / g was used as the equilibrium heat of fusion for 100% crystalline polypropylene. The percent crystallinity of the polypropylene polymer is calculated using the formula [area under the curve (J / g) / 189 (J / g)] * 100.

Blend haze involves adding bis (3,4 dimethylbenzylidene) sorbitol (Millad 3988) to the blend before forming the blend into 1 mm chips, ASTM D 1003 Film haze was measured according to ASTM D 1003.

The gloss was measured at 45 degrees according to ASTM D 2457.

Example 1: Copolymerization continuous polymerization to produce semi-amorphous polypropylene-ethylene copolymer (SAPEC) was conducted in a 9 liter continuous flow stirred tank reactor using hexane as a solvent. The reactor filled with liquid had a residence time of 9 minutes and the pressure was maintained at 700 kPa. The mixed feed of hexane, ethylene and propylene was pre-cooled to about −30 ° C. prior to charging the reactor to remove the heat of polymerization. The catalyst / activator solution in toluene and the scavenger in hexane were charged to the reactor separately and continuously to initiate the polymerization. The reactor temperature was maintained between 35 and 50 ° C., depending on the targeted molecular weight. Depending on the polymerization rate, the temperature of the feed was varied in order to maintain a constant reactor temperature. The polymerization rate was varied between 0.5 kg / hour and 4 kg / hour. Hexane per 30 kg / hour was mixed with 717 g / hour ethylene and / or 5.14 kg / hour propylene and fed to the reactor. The polymerization catalyst, dimethyl silyl bis-indenyl hafnium dimethyl, is N ', N'-dimethyl anilinium-tetrakis (pentafluorophenyl) borate (N', N'-dimethyl anilinium-tetrakis (pentafluorophenyl) borate) at a molar ratio of 1: 1 and activated, and charged at a rate of 0.0135 g / hour. Triisobutyl aluminum diluted solution was used as a scavenger for the catalyst terminator, and the scavenger was added at a rate of about 111 moles per mole of catalyst. After a residence time of 5 degrees with stable polymerization, a representative sample of the polymer produced in this polymerization was collected. The polymer solution was removed from the top of the reactor and distilled with steam to separate the polymer. The polymerization rate was measured as 3.7 kg / hour. The polymer produced by this polymerization had an ethylene content of 14%, a Mooney viscosity ML (1 + 4) of 13.1 at 125 ° C., and an isotactic propylene sequence. Variations in the polymer composition were obtained primarily by changing the ratio of ethylene to propylene. The molecular weight of the polymer was varied by changing the reactor temperature or changing the ratio of total monomer feed to polymerization rate.

The diene was prepared in hexane solution for terpolymerization and the required volume was weighed and added to the mixed feed stream entering the reactor.

Several semi-amorphous propylene ethylene copolymers (SAPEC) were synthesized by the method described in Example 1 above. These are listed in Table 1. Samples SAPEC-I and 2 were used to produce blends for making films.

** MFR value (kg / min) according to ASTM D-1238 Condition L
# GPC data by daltons
* Ethylene weight% measured by IR procedure described above

Semi-amorphous propylene ethylene copolymer, which is derived from a chiral metallocene based catalyst, but has a narrow intramolecular and intermolecular composition distribution. The intermolecular composition distribution of the polymer was determined by thermal fractionation in hexane as follows: about 30 g of crystalline polypropylene-ethylene copolymer cut into small cubes about 1/8 inch (0.32 cm) on that side. And introduced into a thick walled glass jar closed with a screwed lid with 50 mg Irganox 1076 antioxidant (Ciba-Geigy Corpn). 425 ml of hexane (usually the main mixture of isomers and iso-isomers) was added to the contents of the bottle and the bottle was left stoppered at 23 ° C. for 24 hours. After this time, the solution was poured out and the residue was treated with additional hexane and left for a further 24 hours. After this, the two hexane solutions were combined to create a polymer residue that evaporated to dissolve at 23 ° C. Sufficient hexane was added to the residue to a volume of 425 ml and the bottle was placed in a covered circulating water bath at 31 ° C. for 24 hours. The soluble polymer was poured out and additional hexane was added and placed at 31 ° C. for 24 hours before pouring out. This process increased the temperature by about 8 ° C. at each stage, resulting in a semi-amorphous propylene ethylene copolymer portion that was soluble at 40 ° C., 48 ° C., 55 ° C. and 62 ° C. The soluble polymer was dried, weighed, and analyzed for its composition as weight percent of ethylene content by the IR technique described above. Each part obtained by increasing the adjacent temperature is an adjacent part in the above specification. Data on different representative semi-amorphous propylene ethylene copolymers are shown in Tables 2 and 3. The EPR in Table 2 is an ethylene propylene rubber that does not contain a crystallizable propylene species such as a semi-amorphous polymer. This EPR contains 47% ethylene, has a Mooney viscosity (ML 1 + 8 at 127 ° C.) of 28 and a GPC polydispersity (Mw / Mn) of 2.3. This was obtained from ExxonMobil Chemical, Houston, Texas under the trade name Vistalon® 457.

Note: Due to insufficient drying of the polymer parts, in some cases the total of the parts may exceed some 100.

Note: The composition of the polymer in Table 2 was analyzed only for those parts where the total mass was greater than 4%. The experimental accuracy when determining the ethylene content is assumed to be in the range of about 0.4%.

The above semi-amorphous propylene ethylene copolymers SAPEC-1 and SAPEC-2 were combined with a metallocene based propylene homopolymer to produce a blend composition, as described below. SAPEC-1 and SAPEC-2 were first visbreaked prior to melt blending with polypropylene to achieve a melt flow rate of about 20. Visbreaking is a widely used and well accepted procedure for increasing the melt flow rate of polypropylene polymers. This procedure usually involves a certain amount of peroxide (eg 2,5 dimethyl-2,5-di (t-butylperoxy) hexane, obtained as Luperox 101 from AtoFina, Organic Peroxides Divn., Philadelphia, PA. Melt mixing of propylene polymer in the presence of (2,5 dimethyl-2,5-di (t-butyl peroxy) hexane)).

The amount depends on the degree of MFR increase desired. Visbreaking was done in the presence of some polypropylene to further increase crystallinity (a blend of SAPEC and metallocene based propylene homopolymer 60/40). The presence of polypropylene helps to more easily cut the strands into pellets during the extrusion mixing step by allowing the extruded strands to solidify rapidly in a water bath, and to move the pellets freely through the transfer line.

Example 2: Semi-Amorphous Propylene Ethylene Copolymers SAPEC-1 and SAPEC-2 visbreaking The polymer used with the semi-amorphous propylene ethylene copolymer during visbreaking is an MFR of 7.5 dg / min and a metallocene catalyst. Propylene homopolymer with a Mw of 195,000 produced using a pilot scale, two reactors, continuous, stirred tank, bulk liquid phase process. The catalyst used is a rack activated with a silica-bonded activator of N ', N'-diethylaniline-tris (perfluorophenyl) boron Dimethyl dimethyl siladiyl bis (2-methyl-4-phenylindenyl) zirconium dimethyl. The catalyst has a zirconium content of about 0.117% by weight and a boron content of about 0.12% by weight. The reactor was equipped with a jacket to remove the heat of polymerization. The reactor temperature was set at 74 ° C (165F) for the lead reactor and 68 ° C (155F) for the rear reactor. The catalyst was fed at 1.2 g / hour. Triethylaluminum (TEAL: fed to the reactor as a 1 wt% solution in hexane solvent) was used as a scavenger at a level of 20 ppm. The catalyst and activator combined with silica were fed as a 10% slurry in mineral oil and flushed to the reactor with propylene as described above. Propylene monomer was fed to the lead reactor at a rate of 79.5 kg / hr (175 lb / hr) and to the rear reactor at a rate of 30 kg / hr (65 lb / hr). Hydrogen was fed to the lead reactor at 1970 mppm and to the rear reactor at 2220 mppm to control molecular weight. The polymer production rate was 20.5 kg / hr (45 lb / hr) in the lead reactor and 10 kg / hr (22 lb / hr) in the rear reactor. The reactor product was conveyed through a granule processing system to separate and recover the final polymer product. The polymer discharged from the reactor had an MFR of 7.5 dg / min (GPC Mw 195,000, Mw / Mn 2.0, Mz / Mw 1.54). 68% of the final polymer product was from the first stage and 32% was from the second stage. The polymer was melt homogenized and pelletized with 1500 ppm Irganox-2215 (Ciba-Geigy Corporation). Visbreaking was a blend of SAPEC-1 and SAPEC-2 performed with the 7.5 MFR propylene homopolymer discussed above. The blend proportions were 60% by weight SAPEC and 60% by weight propylene homopolymer. Visbreaking was performed on a single screw (60 mm screw diameter; L / D ratio 24; 1; mixing screw) Reifenhauser extruder. The visbreaking experiments are summarized in Table 4.

Both the products of Examples 2-1 and 2-2 contained 60% by weight of semi-amorphous propylene ethylene copolymer. Examples 2-1 and 2-2 were used to make another blend containing different amounts of semi-amorphous propylene ethylene copolymer.

注：PPは、ビスブレーキング操作中に用いられた7.5 dg/分MFRメタロセンホモポリマーを指す。 Example 3 Generation of Semi-Amorphous Propylene Ethylene Copolymer and Polypropylene Homopolymer Blends Examples 2-1 and 2-2 were used to produce several blends as shown in Table 5 at 24 dg / min melt flow. Metallocene-based propylene homopolymer with rate (ASTM 1238, 2.16 kg, 230 ° C), 0.9 g / cc density (ASTM D 792,), and Mw / Mn 2 (ACHIEVE (registered from ExxonMobil Chemical Company, Houston, Texas) (Trade name) obtained under the trade name of 3854).

Note: PP refers to 7.5 dg / min MFR metallocene homopolymer used during visbreaking operation.

Examples 3-1 (33.3% by weight semi-amorphous propylene ethylene copolymer), 3-2 (15% by weight semi-amorphous propylene ethylene copolymer) and 3-3 (27.5% by weight semi-amorphous propylene ethylene) The copolymer blends are all based on semi-amorphous propylene ethylene copolymers containing more than 14% by weight of ethylene (SAPEC-1 and SAPEC-2 in Table 1). This is above the limit of ethylene up to ˜12 wt%, beyond which it is believed that the propylene-ethylene copolymer becomes immiscible in the blend with polypropylene. This incompatibility results in a heterogeneous blend and the semi-amorphous propylene ethylene copolymer is finely dispersed in the polypropylene matrix. A typical example is shown in FIG. FIG. 1 is a plot of tan δ (E ″ / E ′ by DMTA) versus temperature for a blend polymer similar to Example 3-3.

The blend comprises 33.3% by weight semi-amorphous propylene ethylene copolymer and 66.7% by weight semi-crystalline polymer with 14.9% by weight ethylene. The semi-amorphous propylene ethylene copolymer is the same as that used in Example 3-3 (ie SAPEC-1). The figure shows the tan δ response in the β relaxation (ie, Tg) region. Two distinct peaks are observed, corresponding to the respective Tg of polypropylene (0 ° C.) and semi-amorphous propylene ethylene copolymer (−25 ° C.). In the polymer blends of Example 3-2 and Example 3-1, the SAPEC component (ie, SAPEC-2) contains a higher level of ethylene than Example 3-3 (ethylene weight percent is 16.2 weight percent: 14.9 weight percent). weight%). As a result, two similar tanδ reactions are expected. The observation of two tan δ reaction peaks corresponds to the glass temperatures of the semi-amorphous polymer and the semi-crystalline polymer, indicating that the blends of the present invention have heterogeneous properties. A further example showing that the blends of the present invention have heterogeneous properties can be seen in the AFM micrograph shown in FIG. The blend of this figure comprises 20 wt% semi-amorphous propylene ethylene copolymer containing 14.5 wt% ethylene and 80 wt% semicrystalline propylene homopolymer. The photomicrograph shows a fine dispersion of semi-amorphous propylene ethylene copolymer (dark phase) in a matrix of semi-crystalline polymer (light phase).

According to the procedure already described, the permanent set measurement was carried out with a blend composition comprising 33.3% by weight of semi-amorphous propylene ethylene copolymer and 66.7% by weight of semi-crystalline polymer. The semi-amorphous propylene ethylene copolymer contains 14.5 wt% ethylene, which corresponds to SAPEC-1 (14.9 wt% ethylene). This blend had an average permanent set of 187.5% (average of two specimens, with two hysteresis cycles on the Instron instrument for each specimen). A second measurement was made with a blend of 40% by weight of the above semi-amorphous propylene ethylene copolymer and 60% by weight of a semi-crystalline polymer. The average permanent set of this blend was 166.5%.

These high permanent strain values confirm that the blends of the present invention are inelastic.

Example 4: A metallocene based random copolymer used as a comparator of a copolymerized semi-amorphous propylene ethylene copolymer blend to produce a metallocene based random copolymer is a polypropylene copolymer with an MFR of 6.4 dg / min, And Mw produced using a metallocene catalyst with 224,000 was produced on a pilot scale, two reactors, a continuous, stirred tank, bulk liquid phase process. The catalyst is a lacquer dimethylsila activated by a silica-binding activator of N ', N'-diethylaniline-tris (perfluorophenyl) boron. It is bis (2-methyl-4-phenylindenyl) zirconium dimethyl (rac dimethyl siladiyl bis (2-methyl-4-phenylindenyl) zirconium dimethyl). In the catalyst, the proportion of zirconium was about 0.117% by weight and the proportion of boron was about 0.12% by weight. The reactor was equipped with a jacket to remove the heat of polymerization. The reactor temperature was set at 64 ° C (148F) for the lead reactor and 59 ° C (138F) for the rear reactor. The catalyst was fed at a rate of 1.7 g / hour. Triethylaluminum (TEAL: fed to the reactor as a 1 wt% solution in hexane solvent) was used as a scavenger at a level of 20 ppm. The catalyst and activator combined with silica were fed as a 10% slurry in mineral oil and flushed to the reactor with propylene as described above. Propylene monomer was fed to the lead reactor at a rate of 79.5 kg / hr (175 lb / hr) and to the rear reactor at a rate of 30 kg / hr (65 lb / hr). Ethylene was fed to both reactors, and the vapor phase concentration of ethylene in both reactors was about 10 mol%.

Hydrogen was added at 1129 mppm in the lead reactor and 1641 mppm in the rear reactor to control the molecular weight. The polymer production rate was 18.0 kg / hr (39.5 lb / hr) in the lead reactor and 6.4 kg / hr (14.1 lb / hr) in the rear reactor. The reactor product was conveyed through a granule processing system to separate and recover the final polymer product. The polymer discharged from the reactor had an MFR of 6.4 dg / min (GPC Mw 224,000, Mw / Mn 2.0, Mz / Mw 1.68). The ethylene incorporation rate was determined to be 3.3 wt% for the lead reactor product and 3.1 wt% for the later reactor product. Ethylene measured in the final blend product was 3.2% by weight.

74% of the final polymer product was from the first stage and 26% was from the second stage. The polymer showed a DSC melting peak at 127.8 ° C and a DSC crystal peak at 91.23 ° C. The polymer was melted and homogenized by 500 ppm Irganox-2215 (Ciba-Geigy Corporation) and 300 ppm DHT-4A neutralizer (Kyowa Chemical Industry Co., ltd., Osaka, Japan) and extruded as described above. Above, the original MFR6.4 was visbreaked to the final MFR24. The final visbreaked MFR24 product was used as a film production and film test control and was labeled as Example 4.

Example 5: Ziegler-Natta Based Random Copolymer Random Copolymer Granules (Standard Commercial Ziegler-Natta Catalyst, Second Generation, Unsupported Catalyst) Produced in a Commercial Reactor to Make a Ziegler-Natta RCP Control Used as starting material. The product contained 3.0 wt% ethylene as a comonomer. These granules were melted and homogenized with 500 ppm Irganox-2215 stabilizer (Ciba-Geigy Corporation) and 300 ppm DHT-4A neutralizer (Kyowa Chemical Industry Co., ltd., Osaka, Japan), as described above. In the same way, the bisbreaking was performed again from MFR1.0 to MFR24 on the extruder. An ethylene copolymer with an MFR of 24, 3.0% by weight, labeled as Example 5-1, was used as a Ziegler-Natta control.

Another Ziegler-Natta random copolymer control is PD9282 E2 from ExxonMobil Chemical Company, Houston, TX. This marketable product is a standard, supported Ziegler-Natta catalyst. It is a propylene copolymer with a MFR of 5.0 and contains 5.0% ethylene by weight. It usually has a melting point of 133 ° C by DSC. Also includes a set of 1800 ppm Irganox 1010 stabilizer (Ciba-Geigy Corporation), 300 ppm DHT-4A neutralizer, and 1000 ppm anti-tack additive. PD9282 E2 was labeled as Example 5-2.

Example 6: Ziegler-Natta based impact copolymer As an example of a conventional heterogeneous propylene copolymer composition, Ziegler-Natta impact copolymer PP7623 E7 was chosen as a control. This product has an MFR of 7.5 dg / min and a total ethylene content of 9% by weight.

It contains 600 ppm Irganox 1010 stabilizer, 600 ppm Irgafos-168 stabilizer, and 300 ppm DHT-4A neutralizer and is available from ExxonMobil Chemical Company, Houston, TX. PP7623 E7 was labeled as Example 6-1.

Table 6 summarizes the example polymers used to make the films. In addition to the three heterogeneous SAPEC-polypropylene blends discussed above, two Ziegler-Natta RCPs and one Ziegler-Natta ICP, the metallocene homopolymer ACHIEVE 3854 (24 MFR; control) was also examined. ACHIEVE 3854 is a metallocene-based random copolymer with MFR of 24dg / min (ASTM 1238 condition L, 2.16kg, 230 ℃), density of 0.9g / cc (ASTM D792) and Mz / Mw of about 2, ExxonMobil Chemical Company Available from Houston, Texas.

Note: HPP is a propylene homopolymer.

実施例6−1のICP製品のフィルムはBlack-Clawsonフィルムキャストラインで製造された。ラインは2つの、3.5インチ（89 mm）、30/1 L/D押出し機及び1つの2.5インチ（64mm）30/1 L/D押出し機を持つ。各押出し機からのフローは3層Cloeren供給ブロックで組み合わされる。単層フィルムに加え、種々の3層フィルムを作ることが出来る。金型（Extrusion Dies Inc., Chippewa Falls、Wisconsin）は42インチ（106.7 cm）巾で、コートハンガーデザインを用い、ダイリップ（die lip）が調整可能である。15から20ミル（381 から508μm）の金型ギャップが通常のものである。キャスティング部分は30又は36インチ（76から91cm）直径の主冷却ロールを用いる。1500fpm(457 mpm)までのライン速度で、0.4ミル（10μm）から10ミル（254 μm）を超える厚さのフィルムの製造が可能である。 Example 7: Film Production Cast monolayer films formed from most of the polymers in Table 6 were produced on the Killion coextrusion cast film line. The line has three 24: 1 L / D extrusions ("A" extruder is 1 inch, or 25.4 mm diameter; "B" extruder is 0.75 inch, or 19.05 mm diameter; "C" extruder is 0.75 inch, (Or 19.05 mm diameter) polymer is fed to the raw material block. For single layer films, only the “A” extruder was used. The feed block takes the molten polymer from each extruder to a specific channel. The combined flow enters an 8 inch (203.2 mm) wide Cloeren mold. The molten polymer exits the mold and is poured onto a cooled roll (8 inch or 203.2 mm diameter and 10 inch or 254 mm roll surface). The film take-off unit is variable in speed to obtain the desired different thickness of film. Table 7 shows the operating conditions of a typical line producing about 2 mil (50.8 μm) film.

The film of the ICP product of Example 6-1 was produced on a Black-Clawson film cast line. The line has two, 3.5 inch (89 mm), 30/1 L / D extruders and one 2.5 inch (64 mm) 30/1 L / D extruder. The flow from each extruder is combined in a three-layer Cloeren feed block. In addition to single-layer film, various three-layer films can be made. The mold (Extrusion Dies Inc., Chippewa Falls, Wisconsin) is 42 inches (106.7 cm) wide, with a coat hanger design and adjustable die lip. A mold gap of 15 to 20 mils (381 to 508 μm) is normal. The casting part uses a 30 or 36 inch (76 to 91 cm) diameter main cooling roll. Film thicknesses from 0.4 mil (10 μm) to over 10 mil (254 μm) can be produced at line speeds up to 1500 fpm (457 mpm).

Example 8: Film properties The test methods for films with different properties are outlined below. Film properties are usually identified in relation to the stretch of the film (eg, machine direction, MD; or transverse or transverse direction, TD). If the film properties are shown without explicitly indicating the direction of the associated film, i) the directionality is irrelevant (eg, fracture resistance), or ii) the numbers are machine direction and transverse direction Average value.

* Breaking resistance and breaking energy tests were in accordance with ASTM D 5748-95. However, the following shall be changed and applied.

i) Instead of a 0.75 inch diameter pear-shaped TFE-fluorocarbon coated needle (probe), use a 0.75 inch diameter brushed stainless steel deep needle with a matte finish,
ii) Instead of measuring the gauge of each test sample specimen separately, the average gauge measurement value measured on the test sample was used as the gauge value for all destructive measurements measured on that sample.

* ACHIEVE 3854フィルムの落槍衝撃（dart impact） (ASTM D-1709; 26インチ又は、66cmの高さからの落下)数値は47g/ミル（1.85g/μm）である。 The optical properties of 2.0 mil (50.8 μm) cast monolayer films from the polymers and polymer blends in Table 6 are shown in Table 8. All films exhibit low haze, but the films of Examples 3-1 and 3-3 are heterogeneous blend compositions that do not contain fining or nucleating agents, but appear to have the best clarity. Similarly, the gloss of these SAPEC blend films appears to be very good. Table 9 shows the mechanical properties of films of these same polymers (about 2 mils or 50.8 μm).

* ACHIEVE 3854 film dart impact (ASTM D-1709; falling from 26 inches or 66 cm height) The figure is 47 g / mil (1.85 g / μm).

The blend films of Examples 3-1, 3-2 and 3-3 exhibit excellent tear resistance (Elmendorf tear test; ASTM D1922), particularly in the machine direction. The Elmendorf tear resistance does not show a numerical value that is usually compared with polypropylene films. ACHIEVE 3854 and Example 5-1 (Ziegler-Natta RCP) controls (about 30 to about 35 g / mil in the machine direction) are typical values for cast polypropylene films.

Under such a premise, a blend film value having a tear resistance larger than 100 g / mil MD of the present invention was not expected at all. The film of the present invention also exhibits a superior impact strength (total energy impact measured by Kayeness total energy impact tester; ASTM D 4272-99) superior to the controls (Example 5-1 and ACHIEVE 3854). is there. In addition, this film exhibits good tensile properties (ASTM D882), including the low stiffness of the film.

The blend film is compared to Example 5-2 in Table 10. Example 5-2 (5 MFR, 5 wt% ethylene) is another Ziegler-Natta based RCP as in Example 5-1, but with a higher proportion of ethylene comonomer.

From the data in Table 10, this blend film is more tear resistant in the machine direction even when comparable in total ethylene content. The blend film of the present invention exhibits unexpected advantageous properties of low haze, high tear resistance, high impact resistance and relatively low stiffness despite being heterogeneous (heterogeneous) in composition relative to random copolymers. . The film properties of Ziegler-Natta impact copolymers appear to be typical of standard, heterogeneous propylene copolymers. Example 6-1, PP7623 E7 was cast into film on a Black-Clawson cast film line. Film characteristics are:

* Internal haze excludes haze on the film surface. The film surface is coated with an inert liquid recognized by ASTM to eliminate haze due to film surface topology. The procedure for haze measurement is according to ASTM D 1003.

From the data in Table 11, the heterogeneous polymer of Example 6-1 is aggressive to the heterogeneous blends of the present invention in film tear resistance and transparency.

In the literature, Catalloy-based multilayer Ziegler-Nattapropylene polymers have been shown to have high tear strength, especially MD tear resistance. Data can be found in P. Galli's paper “The Future Role of Ziegler-Natta Catalysts (In-situ Flexible Polyolefinic Alloys)” FLEXPO '96 Bulletin, Houston, TX, pages 113-152. This article is incorporated herein by reference. Data for a cast monolayer film of a propylene polymer identified as Adflex® C 200 F is shown in Table 9 of the reference article. A portion of this data, including cast film properties with Adflex C 200 F, was also reproduced in Table 12 below. The only difference from the original data shown in Table 9 of the bibliography is that it contains English entries and / or the meter unit values corresponding to the SI units used in the original table. is there.

Adflex C 200 F is a 6MFR heterogeneous impact copolymer from Basell Polyolefins, Hoofddorp, The Netherlands. The data in Table 12 shows a very low stiffness film, suggesting that the proportion of copolymer rubber is a very high level of composition. Single layer films have outstanding tear and impact resistance and good softness (ie, very low film modulus), but the film haze is very high (greater than 20%). After all, it does not have the characteristics of low haze, high tear resistance, high impact resistance and relatively low stiffness as an example of a heterogeneous SAPEC blend.

All patents, patent applications, test procedures (like ASTM methods), priority documents, papers, publications, manuals and other documents cited in this specification are consistent in their disclosure with the present invention Insofar as and in all legal regimes where such incorporation is permitted, incorporated herein by reference.

When the lower limit of numerical values and the upper limit of numerical values are described, the range from the lower limit of all numerical values to the upper limit of all numerical values is considered.

FIG. 1 is a plot of a Dynamic Mechanical Thermal Analysis (DMTA) test of a blend similar to Example 3-3. This is a plot of tan δ versus temperature for a blend composition comprising 33.3 wt% semi-amorphous propylene-ethylene copolymer and 66.7 wt% semicrystalline propylene homopolymer with 14.9 wt% ethylene. FIG. 2 is an AFM micrograph of a heterogeneous blend composition similar to the blend composition of Example 3-2. This blend comprises 20% by weight semi-amorphous propylene-ethylene copolymer containing 14.5% ethylene and 80% by weight semi-crystalline propylene homopolymer.

Claims (42)

A film comprising a heterogeneous blend, wherein the blend is:
1) 60 to 99% by weight of one or more semi-crystalline polymers (based on the weight of semi-crystalline and semi-amorphous polymers), each semi-crystalline polymer being propylene and 0 to 5% by weight alpha olefin Comonomer (based on the weight of the polymer), each of the semi-crystalline polymers having a melting point of 100 to 170 ° C. and a melt flow rate of 200 dg / min or less; and 2) 1 to 40% by weight of one or more semi-non-polymers Crystalline polymers (based on the weight of semi-crystalline and semi-amorphous polymers), each semi-amorphous polymer being propylene and 10 to 25% by weight of one or more C ₂ and / or C ₄ to C ₁₀ Each of the semi-amorphous polymers comprising an alpha olefin comonomer:
a) heat of fusion from 4 to 70 J / g,
b) Melt flow rate from 0.1 to 200 dg / min,
c) More than 85% of the weight of the polymer is separated as one or two adjacent, soluble parts, the remaining part of the polymer directly preceding or following it; each of these parts being Intermolecular composition distribution determined by thermal fractionation in hexane, with a comonomer content of weight percent in the range not exceeding 20 weight percent compared to the average weight percent of copolymer comonomer content,
d) 1.5 to 4 Mw / Mn,
e) Propylene triadic stereoregularity measured by ^l3 C NMR, 75% or more,
Have
The blend is:
i) a melt flow rate of 0.5 to 100 dg / min, and
ii) 0 to 5 wt% filler based on the weight of polymer and filler, and
iii) less than 20% haze measured with a 1 mm thick injection molded tip, and
iv) permanent set greater than 65%;
And the film is 0.1 to 25 mils (2.5 to 635 microns) thick, and
Less than 10% haze,
1-degree secant tensile modulus is 100,000 to 30,000 psi,
Elmendorf tear strength in the machine direction is 45g / mil or more,
Elmendorf tear strength in the transverse direction is 45g / mil or more,
Total impact energy is 3J or more, and
More than 82 gloss of 45 degrees,
With the characteristics of The film of claim 1, wherein the semi-crystalline polymer comprises propylene and 1 to 3 wt% C ₂ to C ₁₀ alpha olefin comonomer. The film of claim 2, wherein the alpha olefin comonomer is selected from the group consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, and decene. The film of claim 2, wherein the alpha olefin comonomer is selected from the group consisting of ethylene, butene, hexene and octene. The film of claim 2, wherein the alpha olefin comonomer is ethylene. The film of claim 1 wherein the semi-crystalline polymer comprises 0 wt% comonomer. The film according to any one of claims 1 to 6, wherein the semi-crystalline polymer has a melting point of 120 to 170 ° C. 8. A film according to any one of the preceding claims, wherein the semicrystalline polymer has a Mw / Mn of 1.5 to 4. Film according to any one of claims 1 to 8 comprising the alpha-olefin comonomer to C ₁₀ wherein the semi-amorphous polymer from C ₂ from propylene and 10 20 wt%. The film of claim 9, wherein the alpha olefin comonomer is selected from the group consisting of ethylene, butene, pentene, hexene, heptene, octene, nonene, and decene. The film of claim 9, wherein the alpha olefin comonomer is selected from the group consisting of ethylene, butene, hexene, and octene. The film of claim 9, wherein the alpha olefin comonomer is ethylene. 13. A film according to any one of the preceding claims, wherein the semi-amorphous polymer has a percent crystallinity of 2 to 25%. 14. A film according to any one of the preceding claims, wherein the semi-amorphous polymer has a melt flow rate of 0.1 to 25 dg / min. The film according to any one of claims 1 to 14, wherein the semi-amorphous polymer has a melting point of 30 to 80 ° C. The film according to any one of claims 1 to 15, wherein the semi-amorphous polymer has a stereoregularity index of 4 to 12. 17. The semi-amorphous polymer has 80% or more propylene triad stereoregularity, preferably 85% or more, preferably 90% or more propylene triad stereoregularity. Film. 18. A film according to any one of the preceding claims, wherein the blend has a haze of 15% or less, preferably 12% or less, preferably 10% or less. 19. A film according to any one of the preceding claims, wherein the film has a gloss of 85 units or more, preferably 89 units or more, preferably 90 units or more. The semi-amorphous polymer comprises 11 to 25% by weight of comonomer and is present at 15 to 40% by weight and the blend is a semi-amorphous polymer of size less than 4 μm in the continuous phase of the semi-crystalline polymer The film has an Elmendorf tear strength in the machine direction of 60 g / mil (2.4 g / μm) or more, haze of 2% or less, 45 degree gloss of 87 units or more, and 1 degree secant. The film according to any one of claims 1 to 19, wherein the modulus is 75,000 psi (517 MPa) or less and the total energy impact is 3 J or more. The semi-amorphous polymer comprises 11 to 25% by weight of comonomer and is present at 25 to 40% by weight, and the blend is a semi-amorphous polymer of size less than 4 μm in the continuous phase of the semi-crystalline polymer The film has a machine direction Elmendorf tear strength of 100 g / mil (2.4 g / μm) or higher, haze of 1.5% or lower, 45 degree gloss of 88 units or higher, and 1 degree secant The film according to any one of claims 1 to 19, having a modulus of 50,000 psi (517 MPa) or less and a total energy impact of 7 J or more. The film according to any one of claims 1 to 21, wherein the blend has a permanent set of 165% or more, preferably 175% or more, preferably 200% or more. 23. The blended 3.18 mm thick injection molded pad has a resistance ΔL to stress whitening of hunter color of 20 or less, preferably 15 or less, preferably 10 or less, preferably 5 or less. Film. The film according to any one of claims 1 to 23, wherein the haze of the film is 4% or less, preferably 3% or less, preferably 2% or less. 24. The film of claim 23, wherein the film has a haze of 5% or less, an MD Elmendorf tear strength of 50 g / mil or more, and a total energy impact of 3 J or more. 24. The film of claim 23, wherein the film has a haze of 2% or less, an MD Elmendorf tear strength of 100 g / mil or more, and a total energy impact of 7 J or more. The film is:
a) Has a haze of 2% or less,
b) Tensile strength at break in the machine direction is greater than 40 MPa,
c) The tensile strength at break in the transverse direction is greater than 40 MPa,
d) The elongation at break in the machine direction is greater than 500%,
e) Elongation at break in the transverse direction is greater than 500%,
f) Elmendorf tear strength in the machine direction is 50 to 150 g / mil,
g) Transverse Elmendorf tear strength of 100 to 400 g / mil
h) fracture resistance of 6 to 10 lb / mil, and
27. A film according to claim 1, wherein the tensile modulus in the machine direction is less than 350 MPa. The film according to any one of claims 1 to 27, wherein the film is a cast film, a blow-molded film, or a laminated film. 29. A film according to any one of claims 1 to 28, wherein the film is coextruded or laminated. 30. A film according to any one of claims 1 to 29, wherein the film has two or more layers. 31. A film according to any one of the preceding claims, wherein the film comprises a core layer comprising a heterogeneous blend. 32. A film according to any one of the preceding claims, wherein the film comprises a skin layer comprising a heterogeneous blend. 33. A film according to any one of claims 1 to 32, wherein the blend of semi-amorphous polymer and semi-crystalline polymer further comprises a plasticizer, preferably a polyalphaolefin, preferably polydecene. The heterogeneous blend may further comprise a slip agent, preferably 50 to 5000 ppm amide having a chemical structure of CH ₃ (CH ₂ ) ₇ CH═CH (CH ₂ ) _X CONH ₂ , where x is from 5 The film according to any one of claims 1 to 33, which is 15. The heterogeneous blend further comprises a fining agent, preferably the fining agent is 10 ppm to 10 wt% (more preferably 25 ppm to 5 wt%, more preferably 50 ppm to 4000 ppm based on the total polymer in the blend composition). Contains phosphoric acid, phosphate ester, sodium benzoate, talc, sorbitol, adipic acid, benzoic acid (or metal salt of these acids), inorganic filler, preferably clarifier is sorbitol based agent, aluminum salt Base agents or sodium salt-based agents, Ziegler-Natta olefin products or other highly crystalline polymers may be included and the preferred fining agent is disodium [2.2.1] heptane bicyclocarboxylate (disodium [ 2.2.1] heptane bicyclodicarboxylate), bis (3,4 dimethylbenzylidene sorbitol), sodium 2,2'-methyl Sodium 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate, (p-chloro, p'-methyl) , Dibenzylidene sorbitol ((p-chloro, p'methyl) dibenzylidene) sorbitol), bis (p-ethylbenzylidene sorbitol), 1,2,3,4-dibenzylidene sorbitol (1,2 1,2,3,4-dibenzylidene sorbitol), 1,2,3,4-di-para-methylbenzylidene sorbitol, and / or aluminum 2,2'- 35. Any one of claims 1 to 34, which is aluminum 2,2'-methylene-bis (4,6-di-tert-butylphenyl) phosphate. The film according to item. The semi-amorphous polymer has an intermolecular composition distribution in which the portion separated as one or two adjacent soluble portions is 85% or more, preferably 90% or more of the weight of the polymer, and the rest of the polymer is Directly preceding or following portions, and each of these portions is 20% by weight (relatively) of the average weight percent of the comonomer of the copolymer, preferably in the range of not more than 10% by weight. The film according to any one of claims 1 to 35, which contains a comonomer. The blend has a semi-amorphous polymer dispersed in a continuous layer of semi-crystalline polymer in a size less than 4 μm, preferably less than 3 μm, preferably less than 2 μm, preferably less than 1 μm The film according to any one of claims 1 to 36, which is dispersed in size. The film according to any one of claims 1 to 37, wherein the film has a haze of 1% or less. The film is laminated to a substrate, preferably the substrate is a nonwoven fabric, paper, polyolefin, wood, cardboard, metal, metal foil, vapor deposition surface, glass and / or glass coating. The film according to item. The film according to any one of claims 1 to 39, wherein the film is laminated on a substrate, and the substrate is coated with an ink, a dye and / or a pigment. A package comprising the film according to any one of claims 1 to 40. A diaper, a medical film, or a packaging film comprising the film according to any one of claims 1 to 40.

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